CN105084336A - Two-phase calcium phosphate material, preparation method thereof, and two-phase calcium phosphate artificial bone ceramic - Google Patents
Two-phase calcium phosphate material, preparation method thereof, and two-phase calcium phosphate artificial bone ceramic Download PDFInfo
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Abstract
The invention discloses a two-phase calcium phosphate material, a preparation method thereof, and a two-phase calcium phosphate artificial bone ceramic, and belongs to the field of biological ceramic materials. The two-phase calcium phosphate artificial bone ceramic is prepared through preparing a beta phase tricalcium phosphate (beta-TCP) and hydroxy apatite (HA) mixture (the two-phase calcium phosphate material) from egg shells and carrying out a sintering process. The beta-TCP and the HA are prepared from the egg shells with abundant sources through a one-step chemical synthesis process, the mass proportions of the beta-TCP and the HA in the two-phase calcium phosphate are controlled through changing the particle dimensions of the egg shells in the hydrothermal synthesis process, and the preparation cost of the two-phase calcium phosphate material is low. The two-phase calcium phosphate ceramic is prepared through a template process under pressureless sintering conditions, and the two-phase calcium phosphate ceramic with different degradation speeds can be prepared through controlling the mass proportions of the beta-TCP and the HA, so different demands of bone defect patients on the degradation period of artificial bone scaffold materials due to individual difference are met.
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 pottery, belong to bioceramic material field.
Background technology
Bone defect healing is one of Orthopedic Clinical common sympton, only the Cranial defect that causes because of all kinds of accident, disease every year of China or bone injury patient about 3,000,000 people.The Cranial defect of small area can rely on the refresh function of body self to be fully recovered; The Cranial defect of larger area then cannot autogenous repairing, may cause " nonunion ", therefore need to use embedded material to help bone tissue restoration and recovery from illness if do not treat.Artificial bone (comprising calcium phosphate ceramic, bone cement and high molecular polymer) is more and more widely used in bone defect healing clinically; Wherein, calcium phosphate ceramic comprises hydroxyapatite (HA), β phase tricalcium phosphate (β-TCP) and both mixtures (two-phase calcium phosphate material), calcium phosphate ceramic is similar to skeleton inorganic salts ingredients, have good biocompatibility, after et al. Ke, synosteosis ability is good; In addition, porous calcium phosphate ceramic also has good osteoconductive potential.In big area bone defect healing, pure phase β-TCP artificial bone scaffold degradation speed in human body is very fast, and some months extremely several years can be degradable, and pure phase HA artificial bone scaffold degradation speed is excessively slow, even within several years, still cannot degrade, these two kinds of timbering materials are all difficult to match with new osteanagenesis speed.Two calcium phosphate phase supports are made up of the mixture of β-TCP and HA, can be regulated the vivo degradation speed of timbering material by the mass percent controlling two-phase, thus solve in HA ceramic body and do not degrade and the too fast problem of β-TCP pottery vivo degradation.The two-phase calcium phosphate material reported is filled a prescription fixing mostly, is difficult to meet because patient individual difference is to the demand of the different degradation speed of artificial bone supporting material.
Summary of the invention
The present invention seeks to and the problem of HA difficult degradation too fast for β-TCP degradation speed in common calcium phosphate artificial bone material, a kind of two-phase calcium phosphate material and preparation method thereof and two-phase calcium phosphate artificial bone pottery are provided, first utilize eggshell with low cost as starting material, the two-phase calcium phosphate material of required β-TCP and the HA composition of preparation, the two-phase calcium phosphate artificial bone stupalith of obtained controlled degradation speed, has important clinical value further.
For achieving the above object, technical scheme of the present invention is as follows:
Prepare a method for two-phase calcium phosphate material, the method take eggshell as starting material, prepares two-phase calcium phosphate material, specifically comprise the steps: by hydro-thermal reaction
(1) remove in eggshell organic: after egg film is peeled off, eggshell is boiled 30 minutes in deionized water, ultrasonic immersion 40 minutes in the NaClO solution of 10wt.% further, with the organic composition in shell breaking, 100 DEG C of oven dry in vacuum drying oven after use washed with de-ionized water.
(2) grinding is sieved: ground in agate mortar by eggshell, uses standard sieve (20,40,100,300 order) to sieve and obtains the egg shell particle of desired size.
(3) two-phase calcium phosphate material is generated by hydro-thermal reaction: by step (2) gained egg shell particle and (NH
4)
2hPO
4solution (strength of solution 0.02-0.5g/ml) is placed in hydrothermal reaction kettle according to the weight proportion mixing of 1:10 ~ 1:20,24-48 hour is reacted at 140-200 DEG C of temperature, now in eggshell, ingredients calcium carbonate all converts β-TCP and HA to, hydro-thermal reaction product is carried out cleaning and drying, obtains the two-phase calcium phosphate material be made up of β-TCP and HA.In gained two-phase calcium phosphate material, the mass percent of β-TCP is 29-78%.
In step (3) hydrothermal reaction process, by changing the size of egg shell particle, can regulate and control the proportion of composing of β-TCP and HA in gained two-phase calcium phosphate material, along with the reduction of egg shell particle size, the content of β-TCP in two-phase calcium phosphate material also reduces.
In step (3) hydrothermal reaction process, 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.By changing hydrothermal temperature, can also regulate and control to generate the speed of reaction of two-phase calcium phosphate material, along with the rising of temperature of reaction, generating rate is accelerated.
Described eggshell starting material, main component is the calcite (magnesium weight percent is 0.35-0.55%) containing magnesium.After sieving to its grinding, selected egg shell particle size range is 1-850 μm.
By the two-phase calcium phosphate material obtained by aforesaid method for the preparation of two-phase calcium phosphate artificial bone pottery (comprising the calcium phosphate porous pottery of two-phase and two calcium phosphate phase ceramic of compact), method is as follows:
The preparation process of the calcium phosphate porous pottery of two-phase is as follows:
By described two-phase calcium phosphate material ball milling 10 hours, mixed with 5wt.% polyvinyl alcohol solution by ball milling gained powder, in every milliliter of polyvinyl alcohol solution, the amount of powder was 0.4-1g, obtains uniform sizing material under agitation condition, by its extrusion packing to 1cm
360ppi polyurethane cellular support in; Then 600 DEG C of sintering in air atmosphere 3 hours, then 1100 DEG C of sintering 1-2 hour are warming up to, the obtained calcium phosphate porous pottery of two-phase, the aperture ~ 50-500 μm of porous ceramics.
The preparation process of two calcium phosphate phase ceramic of compact is as follows:
By described two-phase calcium phosphate material ball milling 10 hours, ball milling gained powder is dripped 5wt.% polyvinyl alcohol solution (according to 1g:0.1ml ratio), after grinding evenly, put into the mould that diameter is 8mm, base substrate is prepared under using oil press 1kN pressure, base substrate is put into corundum crucible and sinter 3 hours air atmosphere 900 DEG C, then 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 effect of the present invention is embodied in:
1, the present invention proposes particle size by controlling starting material eggshell in hydro-thermal reaction (main component be containing magnesian calcite) and hydrothermal temperature thus the β-TCP of preparation Different Weight per-cent and HA mixture (two-phase calcium phosphate material), prepares the two-phase calcium phosphate ceramic (densification or porous ceramics) of different degradation speed further through high temperature sintering.
2, the present invention can realize the two-phase calcium phosphate artificial bone material preparing different degradation speed according to Cranial defect patient individual difference.
Accompanying drawing explanation
Fig. 1 is the X light powder diffraction figure of original Ovum crusta Gallus domesticus.
Fig. 2 is the X light powder diffraction result that different size Ovum crusta Gallus domesticus particle 200 DEG C of hydro-thermal reactions generate product for 24 hours.
Fig. 3 is the calcium phosphate porous ceramic picture of two-phase.
Fig. 4 is the Electron microscopic findings figure of the calcium phosphate porous pottery of two-phase.
Fig. 5 is two calcium phosphate phase ceramic of compact figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing, technical scheme of the present invention is described further.
The present invention take eggshell as starting material, and main component is the calcite (mass percent ~ 94%) containing magnesium, and Fig. 1 is Ovum crusta Gallus domesticus X light powder diffraction figure.First eggshell starting material to be boiled in deionized water and organic matter in eggshell is removed in the process of NaClO solution oxide, the particle of different size is obtained by sieving, further employing hydrothermal synthesis method obtains two-phase calcium phosphate material, it is β phase tricalcium phosphate (β-TCP) and hydroxyapatite (HA) mixture, then utilizes sintering process to prepare two-phase calcium phosphate artificial bone pottery.In obtained two-phase calcium phosphate material, the mass ratio of β-TCP and HA can by changing reactant Ovum crusta Gallus domesticus particle size and hydrothermal temperature regulates and controls.Present invention process flow process is: the eggshell starting material → removal organic matter → grind → hydro-thermal reaction → cleaning-drying → ball milling → sintering that sieves.
Concrete grammar is as follows: peeled off by egg film in eggshell, boil 30 minutes in deionized water, ultrasonic immersion after 40 minutes in 10wt.%NaClO solution further, uses 100 DEG C of oven dry in vacuum drying oven after washed with de-ionized water three times.Eggshell after oven dry uses standard sieve to sieve after grinding in an agate mortar and obtains the egg shell particle of different size.By egg shell particle and (NH
4)
2hPO
4solution (concentration 0.02-0.5g/ml) is placed in hydrothermal reaction kettle according to the weight proportion mixing of 1:10 ~ 1:20, at 140-200 DEG C of reaction 24-48 hour.Utilize washed with de-ionized water after having reacted three times, recycle dehydrated alcohol eccentric cleaning once, then 100 DEG C of oven dry in vacuum drying oven.Particle ball milling after oven dry 10 hours, mixes ball milling gained powder with 5wt.% polyvinyl alcohol solution, and in every milliliter of polyvinyl alcohol solution, the amount of powder is 0.4-1g, obtains uniform sizing material under agitation condition, by its extrusion packing to 1cm
360ppi polyurethane cellular support in; Then 600 DEG C of sintering in air atmosphere 3 hours, then 1100 DEG C of sintering 1-2 hour are warming up to, the obtained calcium phosphate porous pottery of two-phase.Or ball milling gained powder is dripped 5wt.% polyvinyl alcohol solution (according to 1g:0.1ml ratio), after grinding evenly, put into the mould that diameter is 8mm, base substrate is prepared under using oil press 1kN pressure, base substrate is put into corundum crucible and sinter 3 hours air atmosphere 900 DEG C, then be warming up to 1100 DEG C of sintering 1-2 hour obtained two calcium phosphate phase ceramic of compact.
Embodiment 1
Starting material and requirement: Ovum crusta Gallus domesticus and Secondary ammonium phosphate (analytical pure).
Remove organic: peeled off by Ovum crusta Gallus domesticus setting egg(s) film after removing, immerse in boiling water and boil 30 minutes, in 10wt.%NaClO solution, ultrasonic vibration 40 minutes is to remove the impurity of organic matter in Ovum crusta Gallus domesticus and top layer.100 DEG C of oven dry in vacuum drying oven after washed with de-ionized water three times are used after taking out.
Grinding is sieved: cross 20 and 40 mesh sieves after being ground in mortar by the eggshell after removal organic matter, get 20-40 object egg shell particle (size 355-850 μm) as next step hydro-thermal reaction.
Hydro-thermal reaction: by 20-40 order egg shell particle and (NH
4)
2hPO
4solution is placed in hydrothermal reaction kettle according to the weight proportion mixing of 1:15, and 200 DEG C of hydro-thermal reactions 24 hours, in obtained two-phase calcium phosphate material, the mass percent of β-TCP was about 78% (Fig. 2).
Cleaning-drying: the two-phase calcium phosphate material that hydro-thermal reaction is obtained eccentric cleaning three times in deionized water, then in dehydrated alcohol eccentric cleaning once, at 100 DEG C of vacuum dryings.
Ball milling: be medium ball milling 10 hours with dehydrated alcohol by the particle after drying.
Sintering: mixed with 5wt.% polyvinyl alcohol solution by ball milling gained powder, in every milliliter of polyvinyl alcohol solution, the amount of powder is 0.8g, obtains uniform sizing material under agitation condition, by its extrusion packing to 1cm
360ppi polyurethane cellular support in; Then 600 DEG C of sintering in air atmosphere 3 hours, then be warming up to 1100 DEG C of sintering 1 hour, the obtained calcium phosphate porous pottery (Fig. 3, Fig. 4) of two-phase, takes out sample after cooling to room temperature with the furnace.
Embodiment 2
This example will be chosen 40 and 100 mesh sieve and obtain egg shell particle (size 150-355 μm) as starting material, and the mass percent that hydro-thermal reaction obtains β-TCP in two-phase calcium phosphate material is about 70% (Fig. 2).All the other are with embodiment 1.
Embodiment 3
This example will be chosen 100 and 300 mesh sieve and obtain egg shell particle (size 45-150 μm) as starting material, and the mass percent that hydro-thermal reaction obtains β-TCP in two-phase calcium phosphate material is about 45% (Fig. 2).All the other are with embodiment 1.
Embodiment 4
This example will be chosen >300 mesh sieve and obtain egg shell particle as starting material (size <45 μm), and the mass percent that hydro-thermal reaction obtains β-TCP in two-phase calcium phosphate material is about 29% (Fig. 2).All the other are with embodiment 1.
Embodiment 5
This routine hydro-thermal reaction will 140 DEG C of reactions 48 hours.In obtained two-phase calcium phosphate material, the mass percent of β-TCP is about 67%.All the other are with embodiment 1.
Embodiment 6
It is starting material (size 355-850 μm) that this example chooses 20 and 40 mesh sieve acquisition egg shell particles, and the step before all the other sintered ceramics is with embodiment 1.Ceramic post sintering method is as follows: the powder (2g) after ball milling and 5wt.% polyvinyl alcohol solution (according to 1g:0.1ml ratio) are ground evenly, put into the mould that diameter is 8mm, prepare base substrate under using oil press 1kN pressure.Base substrate is put into corundum crucible and sinter 3 hours air atmosphere 900 DEG C, then be warming up to 1100 DEG C of sintering, 1 hour obtained two calcium phosphate phase ceramic of compact (Fig. 5).
Embodiment 7
It is starting material (size 150-355 μm) that this example chooses 40 and 100 mesh sieve acquisition egg shell particles, and the step before all the other sintered ceramics is with embodiment 1, and the mass percent that hydro-thermal reaction obtains β-TCP in two-phase calcium phosphate material is about 70%.Ceramic post sintering process and product are with embodiment 6.
Embodiment 8
This example will be chosen 100 and 300 mesh sieve and obtain egg shell particle as starting material (size 45-150 μm), and the step before all the other sintered ceramics is with embodiment 1, and the mass percent that hydro-thermal reaction obtains β-TCP in two-phase calcium phosphate material is about 45%.Ceramic post sintering process and product are with embodiment 6.
Embodiment 9
This example will be chosen >300 mesh sieve and obtain egg shell particle as starting material (size <45 μm), step before all the other sintered ceramics is with embodiment 1, and the mass percent that hydro-thermal reaction obtains β-TCP in two-phase calcium phosphate material is about 29%.Ceramic post sintering process and product are with embodiment 6.
Claims (8)
1. prepare a method for two-phase calcium phosphate material, it is characterized in that: the method take eggshell as starting material, prepares two-phase calcium phosphate material, specifically comprise the steps: by hydro-thermal reaction
(1) remove in eggshell organic: after egg film is peeled off, eggshell is boiled 30 minutes in deionized water, ultrasonic immersion 40 minutes in 10wt.% chlorine bleach liquor further, use 100 DEG C of oven dry in vacuum drying oven after washed with de-ionized water;
(2) grinding is sieved: ground in agate mortar by eggshell, uses standard sieve to sieve and obtains the egg shell particle of desired size;
(3) two-phase calcium phosphate material is generated by hydro-thermal reaction: by step (2) gained egg shell particle and (NH
4)
2hPO
4solution mixing is placed in hydrothermal reaction kettle, 24-48 hour is reacted at 140-200 DEG C of temperature, now in eggshell, ingredients calcium carbonate all converts β-TCP and HA to, is carried out cleaning and drying by hydro-thermal reaction product, obtains the two-phase calcium phosphate powder be made up of β-TCP and HA.
2. the method preparing two-phase calcium phosphate material according to claim 1, is characterized in that: in step (3) hydrothermal reaction process, described egg shell particle and (NH
4)
2hPO
4solution mixes according to 1:10 ~ 1:20 weight proportion, described (NH
4)
2hPO
4strength of solution is 0.02-0.5g/ml.
3. the method preparing two-phase calcium phosphate material according to claim 1, it is characterized in that: in step (3) hydrothermal reaction process, by changing the size of egg shell particle, the proportion of composing of β-TCP and HA in gained two-phase calcium phosphate material can be regulated and controled, along with the reduction of egg shell particle size, the content of β-TCP in two-phase calcium phosphate material also reduces.
4. the method preparing two-phase calcium phosphate material according to claim 1, it is characterized in that: in step (3) hydrothermal reaction process, 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 preparing two-phase calcium phosphate material according to claim 1, is characterized in that: described eggshell starting material, and main component is the calcite containing magnesium, and magnesium weight percent is 0.35-0.55%; After sieving to its grinding, selected egg shell particle size range is 1-850 μm.
6. utilize a two-phase calcium phosphate material prepared by method described in claim 1, it is characterized in that: in described two-phase calcium phosphate material, the weight percent of β-TCP is 29-78%.
7. the two-phase calcium phosphate artificial bone pottery utilizing two-phase calcium phosphate material described in claim 6 to prepare, is characterized in that: described two-phase calcium phosphate artificial bone pottery is porous ceramics, and preparation process is as follows:
By described two-phase calcium phosphate material ball milling 10 hours, mixed with 5wt.% polyvinyl alcohol solution by ball milling gained powder, in every milliliter of polyvinyl alcohol solution, the amount of powder was 0.4-1g, obtains uniform sizing material under agitation condition, by its extrusion packing to 1cm
360ppi polyurethane cellular support in; Then 600 DEG C of sintering 3 hours in air atmosphere, then be warming up to 1100 DEG C of sintering 1-2 hour, the obtained calcium phosphate porous pottery of two-phase, the aperture ~ 50-500 μm of porous ceramics.
8. the two-phase calcium phosphate artificial bone pottery utilizing two-phase calcium phosphate material described in claim 6 to prepare, is characterized in that: described two-phase calcium phosphate ceramic is ceramic of compact, and preparation process is as follows:
By described two-phase calcium phosphate material ball milling 10 hours, ball milling gained powder is dripped 5wt.% polyvinyl alcohol solution (according to 1g:0.1ml ratio), after grinding evenly, put into the mould that diameter is 8mm, base substrate is prepared under using oil press 1kN pressure, base substrate is put into corundum crucible and sinter 3 hours air atmosphere 900 DEG C, then be warming up to 1100 DEG C of sintering 1-2 hour obtained two calcium phosphate phase ceramic of compact.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293462A (en) * | 2015-12-02 | 2016-02-03 | 杭州电子科技大学 | Method of preparing hydroxyapatite by mechanochemical method |
| CN105343930A (en) * | 2015-11-30 | 2016-02-24 | 中国科学院金属研究所 | Method for preparing degradable artificial bone material from natural magniferous calcite |
| CN105948012A (en) * | 2016-05-05 | 2016-09-21 | 中国科学院金属研究所 | Method for preparing beta-tricalcium phosphate crystal material under low temperature condition |
| CN107176832A (en) * | 2017-03-30 | 2017-09-19 | 苏州鼎安科技有限公司 | Biphasic calcium phosphate composite granule of high temperature solid state reaction synthesis and preparation method thereof |
| CN108298512A (en) * | 2018-05-08 | 2018-07-20 | 西南交通大学 | A kind of preparation method of the adjustable calcium phosphate of phase constituent |
| 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 |
| CN111921011A (en) * | 2020-09-08 | 2020-11-13 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090191111A1 (en) * | 2008-01-29 | 2009-07-30 | Inha-Industry Partnership Institute | Preparation method of calcium phosphate-based ceramic powder and compact thereof |
| 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 |
-
2014
- 2014-05-23 CN CN201410222710.9A patent/CN105084336B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090191111A1 (en) * | 2008-01-29 | 2009-07-30 | Inha-Industry Partnership Institute | Preparation method of calcium phosphate-based ceramic powder and compact thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 王宏等: "不同孔隙率的双相磷酸钙陶瓷降解性能研究", 《功能材料》 * |
| 陈德敏等: "羟磷灰石生物陶瓷的合成与机械性能测定", 《口腔材料器械》 * |
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| CN105343930A (en) * | 2015-11-30 | 2016-02-24 | 中国科学院金属研究所 | Method for preparing degradable artificial bone material from natural magniferous calcite |
| WO2017092540A1 (en) * | 2015-11-30 | 2017-06-08 | 中国科学院金属研究所 | Degradable artificial bone material preparation method by using natural magnesium-containing calcite |
| CN105293462A (en) * | 2015-12-02 | 2016-02-03 | 杭州电子科技大学 | Method of preparing hydroxyapatite by mechanochemical method |
| CN105948012A (en) * | 2016-05-05 | 2016-09-21 | 中国科学院金属研究所 | Method for preparing beta-tricalcium phosphate crystal material under low temperature condition |
| CN107176832A (en) * | 2017-03-30 | 2017-09-19 | 苏州鼎安科技有限公司 | Biphasic calcium phosphate composite granule of high temperature solid state reaction synthesis and preparation method thereof |
| 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 |
| CN108298512A (en) * | 2018-05-08 | 2018-07-20 | 西南交通大学 | A kind of preparation method of the adjustable calcium phosphate of phase constituent |
| 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 |
| CN111921011A (en) * | 2020-09-08 | 2020-11-13 | 西安点云生物科技有限公司 | Artificial bone coated with coating and preparation method 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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