CN105084336B - A kind of two-phase calcium phosphate material and preparation method thereof and two-phase calcium phosphate artificial bone ceramics - Google Patents
A kind of two-phase calcium phosphate material and preparation method thereof and two-phase calcium phosphate artificial bone ceramics Download PDFInfo
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 101
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 74
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 71
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 71
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000000919 ceramic Substances 0.000 title abstract description 30
- 210000000988 bone and bone Anatomy 0.000 title abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 52
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 52
- 210000003278 egg shell Anatomy 0.000 claims abstract description 52
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 239000010420 shell particle Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910021532 Calcite Inorganic materials 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 20
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 20
- 238000005245 sintering Methods 0.000 abstract description 16
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 235000019731 tricalcium phosphate Nutrition 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000004068 calcium phosphate ceramic Substances 0.000 abstract description 6
- 229910000391 tricalcium phosphate Inorganic materials 0.000 abstract description 3
- 229940078499 tricalcium phosphate Drugs 0.000 abstract description 3
- 239000003462 bioceramic Substances 0.000 abstract 1
- 238000005297 material degradation process Methods 0.000 abstract 1
- 238000001272 pressureless sintering Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000000498 ball milling Methods 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 229940068984 polyvinyl alcohol Drugs 0.000 description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010061363 Skeletal injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002639 bone cement Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- Materials For Medical Uses (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of two-phase calcium phosphate material and preparation method thereof and two-phase calcium phosphate artificial bone ceramics, belong to bioceramic material field.β phases tricalcium phosphate (β TCP) and hydroxyapatite (HA) mixture (two-phase calcium phosphate material) are prepared first with egg shell, and two-phase calcium phosphate artificial bone ceramics are further made by sintering process.The present invention is using egg shell as raw material, the raw material sources enrich, β TCP and HA are only made by a step chemical synthesis, and the mass ratio of β TCP and HA in two calcium phosphate phases can be controlled by changing egg shell particle size in Hydrothermal Synthesiss, the preparation cost of the two-phase calcium phosphate material is low.Two-phase calcium phosphate ceramic can be made under the conditions of pressureless sintering using template, by controlling the wherein β TCP two-phase calcium phosphate biological ceramics different with the obtained degradation speed of HA mass ratio, Cranial defect patient is met because of different demands of the individual difference to artificial bone supporting material degradation cycle.
Description
Technical field
The present invention relates to a kind of two-phase calcium phosphate material and preparation method thereof and two-phase calcium phosphate artificial bone ceramics, belong to raw
Thing ceramic material field.
Background technology
Bone defect healing is one of Orthopedic Clinical common sympton, and the only annual bone caused by all kinds of accidents, disease of China lacks
Damage or the people of bone injury patient about 3,000,000.The Cranial defect of small area can be fully recovered by the regeneration function of body itself；It is larger
The Cranial defect of area then can not autogenous repairing, be likely to result in " bone nonunion " if not treating, it is therefore desirable to helped using implantation material
Help bone tissue reparation and recovery from illness.Artificial bone (including calcium phosphate ceramic, bone cement and high molecular polymer) is more and more wider
It is general to be used for clinically bone defect healing；Wherein, calcium phosphate ceramic include hydroxyapatite (HA), β phases tricalcium phosphate (β-TCP) with
And both mixtures (two-phase calcium phosphate material), calcium phosphate ceramic is similar to skeleton inorganic salts ingredients, with good
Synosteosis ability is good after biocompatibility, et al. Ke；In addition, porous calcium phosphate ceramic also has preferable osteoacusis energy
Power.In large area bone defect healing, pure phase β-TCP artificial bone scaffolds degradation speed in human body is very fast, and some months was to several years
Can be degradable, and pure phase HA artificial bone scaffolds degradation speed is excessively slow, or even several years can not still degrade, both timbering materials
All it is difficult to match with new osteanagenesis speed.Two calcium phosphate phase supports are made up of β-TCP and HA mixture, can pass through control
The mass percent of two-phase carrys out the internal degradation speed of adjusting bracket material, so as to solve non-degradable in HA ceramic bodies and β-TCP
The problem of degraded is too fast in ceramic body.The two-phase calcium phosphate material reported is formulated fixation mostly, it is difficult to meet because of individual patients
Demand of the difference to the different degradation speeds of artificial bone supporting material.
The content of the invention
The present invention seeks to too fast for β-TCP degradation speeds in common calcium phosphate artificial bone material, HA difficult degradations asks
Topic is there is provided a kind of two-phase calcium phosphate material and preparation method thereof and two-phase calcium phosphate artificial bone ceramics, first with low cost
Eggshell as raw material, the two-phase calcium phosphate material of β-TCP and HA compositions, is further made controlled degradation speed needed for preparing
Two-phase calcium phosphate artificial bone ceramic material, with important clinical value.
To achieve the above object, technical scheme is as follows：
A kind of method for preparing two-phase calcium phosphate material, this method is, using eggshell as raw material, to be prepared by hydro-thermal reaction
Two-phase calcium phosphate material, specifically includes following steps：
(1) organic matter in eggshell is removed：Eggshell is boiled in deionized water 30 minutes, further existed after egg film stripping
Ultrasound immersion 40 minutes in 10wt.% NaClO solution, except the organic composition in shell breaking, to be cleaned using deionized water
100 DEG C of drying in vacuum drying chamber afterwards.
(2) grinding sieving：Eggshell is ground in agate mortar, obtained using standard screen (20,40,100,300 mesh) sieving
The egg shell particle of size needed for taking.
(3) two-phase calcium phosphate material is generated by hydro-thermal reaction：By egg shell particle obtained by step (2) and (NH4)2HPO4It is molten
Liquid (solution concentration 0.02-0.5g/ml) is according to 1:10~1:20 weight proportion mixing is placed in hydrothermal reaction kettle, in 140-
Reacted 24-48 hours at a temperature of 200 DEG C, now ingredients calcium carbonate is wholly converted into β-TCP and HA in eggshell, and hydro-thermal reaction is produced
Thing is cleaned and dried, and obtains the two-phase calcium phosphate material being made up of β-TCP and HA.In gained two-phase calcium phosphate material, β-
TCP mass percent is 29-78%.
In step (3) hydrothermal reaction process, by changing the size of egg shell particle, two calcium phosphate phase materials of gained can be regulated and controled
β-TCP and HA proportion of composing in material, with the reduction of egg shell particle size, contents of the β-TCP in two-phase calcium phosphate material
Also reduce.
In step (3) hydrothermal reaction process, by changing hydrothermal temperature, gained two-phase calcium phosphate powder can be regulated and controled
Middle β-TCP and HA proportion of composing.By changing hydrothermal temperature, additionally it is possible to the reaction of regulation and control generation two-phase calcium phosphate material
Speed, with the rise of reaction temperature, generating rate is accelerated.
Described eggshell raw material, main component is the calcite containing magnesium (magnesium percentage by weight is 0.35-0.55%).It is right
It is ground after sieving, and selected egg shell particle particle size range is 1-850 μm.
The two-phase calcium phosphate material obtained by the above method is used to prepare two-phase calcium phosphate artificial bone ceramics (including two
Calcium phosphate phase porous ceramics and two calcium phosphate phase ceramic of compact), method is as follows：
The calcium phosphate porous ceramic preparation process of two-phase is as follows：
By the two-phase calcium phosphate material ball milling 10 hours, powder obtained by ball milling is mixed with 5wt.% poly-vinyl alcohol solutions
Close, the amount of powder is to obtain uniform sizing material under 0.4-1g, stirring condition in every milliliter of poly-vinyl alcohol solution, by its extrusion packing extremely
1cm360ppi polyurethane cellular supports in；Then in air atmosphere 600 DEG C sinter 3 hours, then be warming up to 1100 DEG C of burnings
Knot 1-2 hour, the obtained calcium phosphate porous ceramics of two-phase, the aperture of porous ceramics~50-500 μm.
The preparation process of two calcium phosphate phase ceramic of compact is as follows：
By the two-phase calcium phosphate material ball milling 10 hours, 5wt.% poly-vinyl alcohol solutions are added dropwise in powder obtained by ball milling
(according to 1g:0.1ml ratios), after grinding is uniform, in the mould for being put into a diameter of 8mm, using preparing base under hydraulic press 1kN pressure
Body, is put into corundum crucible by base substrate and is sintered 3 hours for 900 DEG C in air atmosphere, then to be warming up to 1100 DEG C of sintering 1-2 hour obtained
Two calcium phosphate phase ceramic of compact.
Compared with prior art, beneficial effects of the present invention are embodied in：
1st, the present invention proposes the particle by controlling raw material eggshell in hydro-thermal reaction (main component is containing magnesian calcite)
Size and hydrothermal temperature so as to prepare β-TCP and the HA mixture (two-phase calcium phosphate material) of different weight percentage,
The two-phase calcium phosphate ceramic (fine and close or porous ceramics) of different degradation speeds is further prepared through high temperature sintering.
2nd, the present invention can realize the two calcium phosphate phase people that different degradation speeds are prepared according to Cranial defect patient individual difference
Work bone material.
Brief description of the drawings
Fig. 1 is the X light powder diffraction figure of original egg shell.
Fig. 2 is the X light powder diffraction result that different 200 DEG C of size egg shell particle hydro-thermal reactions 24 hours generate product.
Fig. 3 is the calcium phosphate porous ceramic picture of two-phase.
Fig. 4 is the calcium phosphate porous ceramic Electron microscopic findings figure of two-phase.
Fig. 5 is two calcium phosphate phase ceramic of compact figures.
Embodiment
Technical scheme is described further with reference to embodiment and accompanying drawing.
The present invention is that, using eggshell as raw material, main component is the calcite (mass percent~94%) containing magnesium, and Fig. 1 is
Egg shell X light powder diffraction figure.First by eggshell raw material pass through deionized water in boil and NaClO solution oxides processing go
Except the organic matter in eggshell, various sizes of particle is obtained by sieving, two-phase phosphorus is further made using hydrothermal synthesis method
Sour calcium material, it is β phases tricalcium phosphate (β-TCP) and hydroxyapatite (HA) mixture, then prepares two-phase using sintering process
Calcium phosphate artificial bone ceramics.β-TCP and HA mass ratio can be by changing reactant in obtained two-phase calcium phosphate material
Egg shell particle size and hydrothermal temperature regulate and control.Present invention process flow is：Eggshell raw material → removal organic matter →
Grind sieving → hydro-thermal reaction → cleaning-drying → ball milling → sintering.
Specific method is as follows：Egg film in eggshell is peeled off, boiled in deionized water 30 minutes, further in 10wt.%
After ultrasound is soaked 40 minutes in NaClO solution, 100 DEG C of drying in vacuum drying chamber after being cleaned three times using deionized water.Dry
Eggshell after dry obtains various sizes of egg shell particle using standard screen sieving after grinding in an agate mortar.By egg shell particle with
(NH4)2HPO4Solution (concentration 0.02-0.5g/ml) is according to 1:10~1:20 weight proportion mixing is placed in hydrothermal reaction kettle,
Reacted 24-48 hours at 140-200 DEG C.Cleaned three times using deionized water after the completion of reaction, recycle absolute ethyl alcohol centrifugation clear
Wash once, then 100 DEG C of drying in vacuum drying chamber.Particle ball milling after drying 10 hours, by powder obtained by ball milling with
5wt.% poly-vinyl alcohol solutions are mixed, and the amount of powder is to obtain equal under 0.4-1g, stirring condition in every milliliter of poly-vinyl alcohol solution
Homogenate material, by its extrusion packing to 1cm360ppi polyurethane cellular supports in；Then in 600 DEG C of sintering 3 in air atmosphere
Hour, then be warming up to 1100 DEG C and sinter 1-2 hour, the obtained calcium phosphate porous ceramics of two-phase.Or powder obtained by ball milling is added dropwise
5wt.% poly-vinyl alcohol solutions are (according to 1g:0.1ml ratios), after grinding is uniform, in the mould for being put into a diameter of 8mm, use oil
Base substrate is prepared under press 1kN pressure, base substrate is put into corundum crucible sinters 3 hours for 900 DEG C in air atmosphere, then is warming up to
Two calcium phosphate phase ceramic of compact are made in 1-2 hours in 1100 DEG C of sintering.
Embodiment 1
Raw material and requirement：Egg shell and diammonium hydrogen phosphate (analysis is pure).
Remove organic matter：Egg film on egg shell is peeled off after removing, boiled 30 minutes in immersion boiling water, in 10wt.%
Ultrasonic vibration 40 minutes is to remove the organic matter in egg shell and the impurity on top layer in NaClO solution.Deionization is used after taking-up
100 DEG C of drying in vacuum drying chamber after water is cleaned three times.
Grinding sieving：20 and 40 mesh sieves are crossed after the eggshell removed after organic matter is ground in mortar, the egg of 20-40 mesh is taken
Shell particle (355-850 μm of size) is used as next step hydro-thermal reaction.
Hydro-thermal reaction：By 20-40 mesh egg shell particle and (NH4)2HPO4Solution is according to 1:15 weight proportion mixing is placed in water
In thermal response kettle, in 200 DEG C of hydro-thermal reactions 24 hours, the mass percent that β-TCP in two-phase calcium phosphate material are made was about
78% (Fig. 2).
It is cleaned and dried：The two-phase calcium phosphate material that hydro-thermal reaction is obtained eccentric cleaning three times in deionized water, then
In absolute ethyl alcohol eccentric cleaning once, in 100 DEG C of vacuum dryings.
Ball milling：By the particle after drying using absolute ethyl alcohol as medium ball milling 10 hours.
Sintering：Powder obtained by ball milling is mixed with 5wt.% poly-vinyl alcohol solutions, powder in every milliliter of poly-vinyl alcohol solution
Amount be 0.8g, uniform sizing material is obtained under stirring condition, by its extrusion packing to 1cm360ppi polyurethane cellular supports in；
Then in air atmosphere 600 DEG C sinter 3 hours, then be warming up to 1100 DEG C and sinter 1 hour, two-phase calcium phosphate porous pottery is made
Porcelain (Fig. 3, Fig. 4), cools to the furnace and sample is taken out after room temperature.
Embodiment 2
This example will choose 40 and 100 mesh sieves and obtain egg shell particle (150-355 μm of size) as raw material, and hydro-thermal is anti-
The mass percent that β-TCP in two-phase calcium phosphate material should be made is about 70% (Fig. 2).Remaining be the same as Example 1.
Embodiment 3
This example will choose 100 and 300 mesh sieves and obtain egg shell particle (45-150 μm of size) as raw material, and hydro-thermal is anti-
The mass percent that β-TCP in two-phase calcium phosphate material should be made is about 45% (Fig. 2).Remaining be the same as Example 1.
Embodiment 4
This example will be chosen>300 mesh sieves obtain egg shell particle and are used as raw material (size<45 μm), hydro-thermal reaction is made
β-TCP mass percent is about 29% (Fig. 2) in two-phase calcium phosphate material.Remaining be the same as Example 1.
Embodiment 5
This example hydro-thermal reaction will react 48 hours at 140 DEG C.The mass percent of β-TCP in two-phase calcium phosphate material is made
About 67%.Remaining be the same as Example 1.
Embodiment 6
It is raw material (355-850 μm of size) that this example, which chooses 20 and 40 mesh sieves and obtains egg shell particle, remaining sintering pottery
Step be the same as Example 1 before porcelain.Ceramic post sintering method is as follows：By the powder (2g) after ball milling and 5wt.% poly-vinyl alcohol solutions
(according to 1g:0.1ml ratios) after grinding is uniform, in the mould for being put into a diameter of 8mm, using preparing base under hydraulic press 1kN pressure
Body.Base substrate is put into corundum crucible to sinter 3 hours for 900 DEG C in air atmosphere, then is warming up to 1100 DEG C of sintering and is made two within 1 hour
Calcium phosphate phase ceramic of compact (Fig. 5).
Embodiment 7
It is raw material (150-355 μm of size) that this example, which chooses 40 and 100 mesh sieves and obtains egg shell particle, remaining sintering pottery
Step be the same as Example 1 before porcelain, the mass percent that β-TCP in two-phase calcium phosphate material are made in hydro-thermal reaction is about 70%.Pottery
Porcelain sintering process and product be the same as Example 6.
Embodiment 8
This example will choose 100 and 300 mesh sieves and obtain egg shell particle as raw material (45-150 μm of size), remaining burning
β-TCP mass percent is about in step be the same as Example 1 before knot ceramics, the obtained two-phase calcium phosphate material of hydro-thermal reaction
45%.Ceramic post sintering process and product be the same as Example 6.
Embodiment 9
This example will be chosen>300 mesh sieves obtain egg shell particle and are used as raw material (size<45 μm), remaining sintering ceramics
Preceding step be the same as Example 1, the mass percent that β-TCP in two-phase calcium phosphate material are made in hydro-thermal reaction is about 29%.Ceramics
Sintering process and product be the same as Example 6.
Claims (5)
1. a kind of method for preparing two-phase calcium phosphate material, it is characterised in that：This method is, using eggshell as raw material, to pass through hydro-thermal
Reaction prepares two-phase calcium phosphate material, specifically includes following steps：
(1) organic matter in eggshell is removed：Eggshell is boiled in deionized water 30 minutes, further existed after egg film stripping
Ultrasound immersion 40 minutes in 10wt.% liquor natrii hypochloritises, 100 DEG C of bakings in vacuum drying chamber after being cleaned using deionized water
It is dry；
(2) grinding sieving：Eggshell is ground in agate mortar, the egg shell particle for size needed for obtaining of being sieved using standard screen；
(3) two-phase calcium phosphate material is generated by hydro-thermal reaction：By egg shell particle obtained by step (2) and (NH4)2HPO4Solution is mixed
Conjunction is placed in hydrothermal reaction kettle, is reacted at a temperature of 140-200 DEG C 24-48 hours, now ingredients calcium carbonate all turns in eggshell
Change β-TCP and HA into, hydro-thermal reaction product is cleaned and dried, obtain two calcium phosphate phase powder being made up of β-TCP and HA
End.
2. the method according to claim 1 for preparing two-phase calcium phosphate material, it is characterised in that：Step (3) hydro-thermal reaction
During, the egg shell particle and (NH4)2HPO4Solution is according to 1:10~1:20 weight proportions are mixed, (the NH4)2HPO4It is molten
Liquid concentration is 0.02-0.5g/ml.
3. the method according to claim 1 for preparing two-phase calcium phosphate material, it is characterised in that：Step (3) hydro-thermal reaction
During, by changing the size of egg shell particle, the ratio of components of β-TCP and HA in gained two-phase calcium phosphate material can be regulated and controled
Example, with the reduction of egg shell particle size, contents of the β-TCP in two-phase calcium phosphate material is also reduced.
4. the method according to claim 1 for preparing two-phase calcium phosphate material, it is characterised in that：Step (3) hydro-thermal reaction
During, by changing hydrothermal temperature, the proportion of composing of β-TCP and HA in gained two-phase calcium phosphate powder can be regulated and controled.
5. the method according to claim 1 for preparing two-phase calcium phosphate material, it is characterised in that：Described eggshell former material
Material, main component is the calcite containing magnesium, and magnesium percentage by weight is 0.35-0.55%；It is ground after sieving, selected egg
Shell grain graininess scope is 1-850 μm.
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| CN105343930B (en) * | 2015-11-30 | 2019-01-22 | 中国科学院金属研究所 | The method for preparing degradable artificial bone material using the calcite naturally containing magnesium |
| CN105293462A (en) * | 2015-12-02 | 2016-02-03 | 杭州电子科技大学 | Method of preparing hydroxyapatite by mechanochemical method |
| CN105948012B (en) * | 2016-05-05 | 2020-02-18 | 中国科学院金属研究所 | Method for preparing β phase tricalcium phosphate crystal material under low temperature condition |
| 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 |
| CN108298512B (en) * | 2018-05-08 | 2020-09-22 | 西南交通大学 | Preparation method of phase-component-adjustable calcium phosphate |
| CN109095446A (en) * | 2018-08-27 | 2018-12-28 | 上海应用技术大学 | A kind of biophasic calcium phosphate ceramic material and preparation method thereof |
| CN111085158A (en) * | 2019-12-23 | 2020-05-01 | 暨南大学 | Method for preparing defluorination water purifying agent by using eggshells and application thereof |
| CN111921011B (en) * | 2020-09-08 | 2022-07-19 | 西安点云生物科技有限公司 | Artificial bone coated with coating and preparation method thereof |
| CN115572177A (en) * | 2021-07-05 | 2023-01-06 | 陈月端 | Bone filler prepared from natural calcium-containing waste and preparation method thereof |
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| CN102070131A (en) * | 2010-11-16 | 2011-05-25 | 中国矿业大学 | Method for synthesizing high-purity hydroxyapatite (HA) from eggshells under hydrothermal condition |
| CN102727937A (en) * | 2012-06-28 | 2012-10-17 | 哈尔滨工程大学 | Biodegradable zinc (or zinc alloy) and porous biphase calcium phosphate composite material and preparation method thereof |
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| CN102070131A (en) * | 2010-11-16 | 2011-05-25 | 中国矿业大学 | Method for synthesizing high-purity hydroxyapatite (HA) from eggshells under hydrothermal condition |
| CN102727937A (en) * | 2012-06-28 | 2012-10-17 | 哈尔滨工程大学 | Biodegradable zinc (or zinc alloy) and porous biphase calcium phosphate composite material and preparation method thereof |
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