CN108525004A - Alpha-semi water plaster stone/hydroxyapatite composite microspheres and preparation method thereof - Google Patents
Alpha-semi water plaster stone/hydroxyapatite composite microspheres and preparation method thereof Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The present invention provides a kind of αsemiwatergypsum/hydroxyapatite composite microspheres and preparation method thereof, and preparation method includes：Distilled water, super cladodification polyethyleneimine, calcium salt and dihydrate gypsum is added in step 1. in the reaction vessel, is sufficiently stirred, and adjusts pH value 4.5~6.5, obtains suspension；Step 2. heats suspension to 90~97 DEG C, reacts 3~5h, adds disodium hydrogen phosphate, and it is 10 to adjust pH value, then in 80~85 DEG C of 8~15h of isothermal reaction, complex microsphere slurries；Step 3. filters complex microsphere slurries, and solid is washed 2~3 times with absolute ethyl alcohol, dry to get αsemiwatergypsum/hydroxyapatite composite microspheres.The complex microsphere of large specific surface area, stable structure can be prepared by simple process by this method, and can be according to the different content of hydroxyapatite in microballoon, to adjust the degradation property of composite microsphere material.
Description
Technical field
The invention belongs to bio-medical material preparation fields, and in particular to a kind of alpha-semi water plaster stone/hydroxyapatite is compound
Microballoon and preparation method thereof.
Technical background
Now, bone defect case is more and more caused by wound, infection or other bone diseases, from diaphysis and different diaphysis
Quantity far can not meet the clinical needs to bone collection, it is therefore, clinical increasing to artificial bone alternate material demand.
In order to meet different application demands, researchers have prepared the alternative materials of variform.In these materials, microballoon material
Material has many advantages, such as that good mobility and injection property, intensity are high, is not easy to reunite and receive more and more attention.
Alpha-semi water plaster stone is a kind of bone defect filling renovation material being widely recognized as, possesses good biocompatibility
And osteoconductive.But alpha-semi water plaster stone, due to degradation in vivo excessive velocities, partially short degradation soak time (is usually 6~8
Week), degradation speed is significantly greater than new bone growth speed.Therefore, alpha-semi water plaster stone directly applies to clinic and will be subject to certain restrictions.
Hydroxyapatite is a kind of important inorganic component part in skeleton and tooth, has good bio-compatible
Property, bioactivity and bone conduction effect, be clinically widely used in the reparation and replacement of biological hard tissue, be that good bone lacks
Damage repair materials.However, one of the major defect of hydroxyapatite is that internal degradation speed is partially slow, assimilation effect is poor, implantation
Growing into for new bone is affected in vivo.
Alpha-semi water plaster stone degradation speed is too fast, and hydroxyapatite degradation speed is partially slow, if both substances directly make
With the reparation and replacement for being unfavorable for bone tissue.In order to prepare the excellent composite material of biological property, Chinese invention patent is (specially
Profit number：ZL200710063903.4 a kind of novel bone grafting material) is disclosed, by alpha-semi water plaster stone and bata-tricalcium phosphate by centainly matching
Than composition；Chinese invention patent (application number 201110416270.7) discloses a kind of hydroxyapatite packet with nucleocapsid
Alpha-semi water plaster stone composite particles are wrapped up in, which has certain application prospect in terms of Bone Defect Repari；Chinese invention patent (application
It number 201010185090.8) discloses a kind of alpha-semi water plaster stone and the composite bone repairing material to be formed is blended in hydroxyapatite, be worth
It obtains, it is noted that alpha-semi water plaster stone and hydroxyapatite are simple mixing, the comprehensive performance of repair materials in the patent
Do not regulated and controled effectively.In addition, the preparation condition of the patent is high temperature, high energy consumption is unfavorable for industrial production.
Invention content
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide a kind of alpha-semi water plaster stone/hydroxy-apatite
Stone complex microsphere and preparation method thereof can prepare the α-half water stones of large specific surface area, stable structure by simple process
Cream/hydroxyapatite composite microspheres, and can be according to the different content of hydroxyapatite in microballoon, to adjust composite microsphere material
Degradation property.
The present invention to achieve the goals above, uses following scheme：
<Preparation method>
The present invention provides a kind of preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres, which is characterized in that including
Following steps：Distilled water, super cladodification polyethyleneimine, calcium salt and two is added in step 1. in the reaction vessel equipped with agitating device
Water gypsum, is sufficiently stirred, and it is 4.5~6.5 to adjust pH value, obtains suspension；Step 2. heats suspension to 90~97 DEG C, reacts
After 3~5h, disodium hydrogen phosphate Na is added2HPO4·12H2O, adjust pH value be 10, then 80~85 DEG C of isothermal reactions 8~
15h obtains alpha-semi water plaster stone/hydroxyapatite composite microspheres slurries；Step 3. is by alpha-semi water plaster stone/hydroxyapatite composite microspheres
Slurries filter, and solid is washed 2~3 times with absolute ethyl alcohol, dry to get alpha-semi water plaster stone/hydroxyapatite composite microspheres.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 1, mass concentration of the super cladodification polyethyleneimine in suspension is preferably 0.5~2.0%.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 1, calcium salt is Ca (Cl)2With Ca (NO3)2Any one of or two kinds of mixture, and its
Mass concentration in suspension is preferably 5~25%.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 1, in suspension, the mass concentration of dihydrate gypsum is preferably 20~40%.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 1, it is preferred to use dilute sulfuric acid adjusts pH value.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 2, the disodium hydrogen phosphate of addition and the molar ratio of calcium salt are preferably 1:0.6~5.5.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 2, it is preferred to use the sodium hydroxide solution of a concentration of 1mol/L adjusts pH value.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 2, mixing speed is preferably 150~180r/min.
Further, the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres provided by the invention can also have
There are following characteristics：In step 3, drying condition is preferably：Dry 2~4h under the conditions of 45~60 DEG C.
<Complex microsphere>
The present invention also provides a kind of alpha-semi water plaster stone/hydroxyapatite composite microspheres, it is characterised in that：Using above-mentioned<System
Preparation Method>Described in method be prepared.
The effect of invention
This method is regulation and control template with super cladodification polyethyleneimine, is with dihydrate gypsum, disodium hydrogen phosphate and inorganic calcium salt
Primary raw material prepares large specific surface area by co-precipitation, has good injection property and high compactedness, the α-half of stable structure
Water gypsum/hydroxyapatite composite microspheres.In the preparation process of complex microsphere, dihydrate gypsum is first in inorganic calcium salt solution
Conversion forms alpha-semi water plaster stone crystallite presoma.Then, inorganic calcium salt and the disodium hydrogen phosphate of addition generate hydroxyapatite, α-
Semi-hydrated gypsum crystallite presoma is gradually grown up during the reaction, and forms co-precipitation with the hydroxyapatite of generation, super
Microballoon is formed under the effect of cladodification polyethyleneimine template molecule.The content of hydroxyapatite, mainly passes through phosphorus in complex microsphere
The ratio of sour disodium hydrogen, inorganic calcium salt and dihydrate gypsum is regulated and controled.With the increase of ratio, hydroxyapatite is in complex microsphere
In content be also gradually increased, the degradation speed of composite microsphere material also can be slack-off therewith.In addition, this method is simple for process, behaviour
Facilitate, is very suitable for industrialization.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the alpha-semi water plaster stone/hydroxyapatite composite microspheres prepared in embodiment one；
Fig. 2 is the scanning electron microscope part inside the alpha-semi water plaster stone/hydroxyapatite composite microspheres prepared in embodiment one
Enlarged drawing；
Fig. 3 is the XRD diagram of the alpha-semi water plaster stone/hydroxyapatite composite microspheres prepared in embodiment one；
Fig. 4 is the energy spectrum diagram of the alpha-semi water plaster stone/hydroxyapatite composite microspheres prepared in embodiment one.
Specific implementation mode
Below in conjunction with attached drawing to alpha-semi water plaster stone/hydroxyapatite composite microspheres of the present invention and preparation method thereof
Specific embodiment is described in detail.Super cladodification polyethyleneimine employed in following embodiment is Aldrich public affairs
Take charge of the product of production, Mn=20000g/mol, degree of grafting DB=60, monodispersity index PDI=2.1.
<Embodiment one>
Preparation method：
500ml distilled water, the super cladodification polyethyleneimines of 8g, 50g are added in the reaction vessel equipped with agitating device
CaCl2It with 300g dihydrate gypsums, is sufficiently stirred, the dilute hydrochloric acid for being 25% with mass concentration adjusts pH value 5.0 and obtains suspension, heating
Suspension is to 95 DEG C, after isothermal reaction 3.5h.Under stirring, 35g disodium hydrogen phosphates (Na is added2HPO4·12H2O),
And the sodium hydroxide solution of a concentration of 1mol/L is slowly added dropwise, until pH value reaches 10.Continue constant temperature and react 10h at 85 DEG C, instead
After answering, the product after reaction is filtered, solid is washed 2 times with absolute ethyl alcohol, dry 3h under the conditions of 50 DEG C of drying box constant temperature,
Up to alpha-semi water plaster stone/hydroxyapatite composite microspheres.
Sample characterization：
As shown in Figure 1, the alpha-semi water plaster stone prepared in the present embodiment one/hydroxyapatite composite microspheres average grain diameter is about
200μm.It is mainly accumulated by the arrangement in good order of six side's short cylinder alpha-semi water plaster stone crystal, hydroapatite particles are dispersed in
Between alpha-semi water plaster stone crystal.As shown in Fig. 2, can be seen that microballoon from damaged microballoon has hollow structure, hydroxyapatite
It is particle studded on alpha-semi water plaster stone crystal, form co-precipitation.Fig. 3 b and Fig. 4 b are respectively the XRD and energy stave of complex microsphere
Sign in XRD spectra and energy spectrum diagram as a result, have apparent alpha-semi water plaster stone and hydroxyapatite characteristic peak to occur, furtherly
Bright complex microsphere is made of alpha-semi water plaster stone crystal and hydroxyapatite.Fig. 3 a and Fig. 4 a analyze pure alpha-semi water plaster stone
XRD and power spectrum characterization result.To analyze pure alpha-semi water plaster stone and analysis pure ha standard curve, profit are formulated as standard specimen
With XRD quantitative analysis methods, the content of hydroxyapatite in complex microsphere is analyzed, as a result shows the content of hydroxyapatite in microballoon
It is 9.87%.<Embodiment two>
Preparation method：
500ml distilled water, the super cladodification polyethyleneimines of 7g, 80g are added in the reaction vessel equipped with agitating device
CaCl2It with 300g dihydrate gypsums, is sufficiently stirred, adjusting pH value 5.5 with dilute sulfuric acid obtains suspension, and heating suspension is permanent to 95 DEG C
After temperature reaction 3.5h.Under stirring, 60g disodium hydrogen phosphates (Na is added2HPO4·12H2O), and it is slowly added dropwise a concentration of
The sodium hydroxide solution of 1mol/L, until pH value reaches 10.Continue constant temperature and react 10h at 85 DEG C, after reaction, after reaction
Product filter, solid wash 2 times with absolute ethyl alcohol, and 3h is dried under the conditions of 50 DEG C of drying box constant temperature to get alpha-semi water plaster stone/hydroxyl
Base apatite complex microsphere.
Sample characterization：
The complex microsphere average grain diameter prepared in the present embodiment two is about 180 μm.Microballoon is by hydroxyapatite and α-half water
Gypsum crystal is co-precipitated the hollow structure to be formed.Using the XRD quantitative analysis methods in such as embodiment 1, hydroxyl in complex microsphere is analyzed
The content of base apatite is it is found that the content of hydroxyapatite is 15.11% in the microballoon prepared under the conditions of this.
<Embodiment three>
Preparation method：
500ml distilled water, the super cladodification polyethyleneimines of 10g, 100g are added in the reaction vessel equipped with agitating device
CaCl2It with 320g dihydrate gypsums, is sufficiently stirred, adjusting pH value 6.0 with dilute sulfuric acid obtains suspension, and heating suspension is permanent to 95 DEG C
After temperature reaction 4.0h.Under stirring, 100g disodium hydrogen phosphates (Na is added2HPO4·12H2O), and concentration is slowly added dropwise
For the sodium hydroxide solution of 1mol/L, until pH value reaches 10.Continuation constant temperature reacts 12h at 80 DEG C will react after reaction
Rear product filters, and solid wash 2 times with absolute ethyl alcohol, dried under the conditions of 60 DEG C of drying box constant temperature 2h to get alpha-semi water plaster stone/
Hydroxyapatite composite microspheres.
Sample characterization：
The complex microsphere average grain diameter prepared in the present embodiment three is about 200 μm.Microballoon is by hydroxyapatite and α-half water
Gypsum crystal is co-precipitated the hollow structure to be formed.Using the XRD quantitative analysis methods in such as embodiment 1, hydroxyl in complex microsphere is analyzed
The content of base apatite is it is found that the content of hydroxyapatite is 21.26% in the microballoon prepared under the conditions of this.
<Example IV>
Preparation method：
500ml distilled water, the super cladodification polyethyleneimines of 10g, 120g are added in the reaction vessel equipped with agitating device
CaCl2It with 350g dihydrate gypsums, is sufficiently stirred, adjusting pH value 5.5 with dilute sulfuric acid obtains suspension, and heating suspension is permanent to 97 DEG C
After temperature reaction 3.5h.Under stirring, 100g disodium hydrogen phosphates (Na is added2HPO4·12H2O), and concentration is slowly added dropwise
For the sodium hydroxide solution of 1mol/L, until pH value reaches 10.Continuation constant temperature reacts 14h at 80 DEG C will react after reaction
Rear product filters, and solid wash 2 times with absolute ethyl alcohol, dried under the conditions of 50 DEG C of drying box constant temperature 3h to get alpha-semi water plaster stone/
Hydroxyapatite composite microspheres.
Sample characterization：
The complex microsphere average grain diameter prepared in the present embodiment four is about 200 μm.Microballoon is by hydroxyapatite and α-half water
Gypsum crystal is co-precipitated the hollow structure to be formed.Using the XRD quantitative analysis methods in such as embodiment 1, hydroxyl in complex microsphere is analyzed
The content of base apatite is it is found that the content of hydroxyapatite is 28.75% in the microballoon prepared under the conditions of this.
<Embodiment five>
Preparation method：
500ml distilled water, the super cladodification polyethyleneimines of 7g, 150g Ca are added in the reaction vessel equipped with agitating device
(NO3)2It with 300g dihydrate gypsums, is sufficiently stirred, adjusting pH value 4.5 with dilute sulfuric acid obtains suspension, and heating suspension is permanent to 95 DEG C
After temperature reaction 4.5h.Under stirring, 200g disodium hydrogen phosphates (Na is added2HPO4·12H2O), and concentration is slowly added dropwise
For the sodium hydroxide solution of 1mol/L, until pH value reaches 10.Continuation constant temperature reacts 15h at 80 DEG C will react after reaction
Rear product filters, and solid wash 2 times with absolute ethyl alcohol, dried under the conditions of 50 DEG C of drying box constant temperature 3h to get alpha-semi water plaster stone/
Hydroxyapatite composite microspheres.
Sample characterization：
The complex microsphere average grain diameter prepared in the present embodiment five is about 150 μm.Microballoon is by hydroxyapatite and α-half water
Gypsum crystal is co-precipitated the hollow structure to be formed.Using the XRD quantitative analysis methods in such as embodiment 1, hydroxyl in complex microsphere is analyzed
The content of base apatite is it is found that the content of hydroxyapatite is 32.28% in the microballoon prepared under the conditions of this.
<Embodiment six>
Preparation method：
500ml distilled water, the super cladodification polyethyleneimines of 10g, 80g Ca are added in the reaction vessel equipped with agitating device
(NO3)2It with 350g dihydrate gypsums, is sufficiently stirred, adjusting pH value 5.5 with dilute sulfuric acid obtains suspension, and heating suspension is permanent to 95 DEG C
After temperature reaction 4.0h.Under stirring, 120g disodium hydrogen phosphates (Na is added2HPO4·12H2), O and concentration is slowly added dropwise
For the sodium hydroxide solution of 1mol/L, until pH value reaches 10.Continuation constant temperature reacts 13h at 80 DEG C will react after reaction
Rear product filters, and solid wash 2 times with absolute ethyl alcohol, dried under the conditions of 50 DEG C of drying box constant temperature 3h to get alpha-semi water plaster stone/
Hydroxyapatite composite microspheres.
Sample characterization：
The complex microsphere average grain diameter prepared in the present embodiment six is about 180 μm.Microballoon is by hydroxyapatite and α-half water
Gypsum crystal is co-precipitated the hollow structure to be formed.Using the XRD quantitative analysis methods in such as embodiment 1, hydroxyl in complex microsphere is analyzed
The content of base apatite is it is found that the content of hydroxyapatite is 14.35% in the microballoon prepared under the conditions of this.
Above example is only the illustration done to technical solution of the present invention.α-half water stone according to the present invention
Cream/hydroxyapatite composite microspheres and preparation method thereof are not merely defined in described content in the embodiment above, and
It is to be subject to claim limited range.What those skilled in the art of the invention were done on the basis of the embodiment appoints
What modify or supplement or equivalence replacement, all in the claim range claimed of the present invention.
Claims (10)
1. a kind of preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres, which is characterized in that include the following steps：
Distilled water, super cladodification polyethyleneimine, calcium salt and dihydrate gypsum is added in step 1. in the reaction vessel, is sufficiently stirred, and adjusts
It is 4.5~6.5 to save pH value, obtains suspension；
Step 2. heats suspension to 90~97 DEG C, after reacting 3~5h, adds disodium hydrogen phosphate Na2HPO4·12H2O is adjusted
PH value is 10, then in 80~85 DEG C of 8~15h of isothermal reaction, obtains alpha-semi water plaster stone/hydroxyapatite composite microspheres slurries；
Step 3. filters alpha-semi water plaster stone/hydroxyapatite composite microspheres slurries, and solid is washed with absolute ethyl alcohol, dry, i.e.,
Obtain alpha-semi water plaster stone/hydroxyapatite composite microspheres.
2. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 1, mass concentration of the super cladodification polyethyleneimine in suspension is 0.5~2.0%.
3. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 1, calcium salt is Ca (Cl)2With Ca (NO3)2Any one of or two kinds of mixture, and it is outstanding
Mass concentration in turbid is 5~25%.
4. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 2, it is characterised in that：
Wherein, in step 1, in suspension, the mass concentration of dihydrate gypsum is 20~40%.
5. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 1, pH value is adjusted using dilute sulfuric acid.
6. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 2, the molar ratio of the disodium hydrogen phosphate and calcium salt of addition is 1:0.6~5.5.
7. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 2, pH value is adjusted using the sodium hydroxide solution of a concentration of 1mol/L.
8. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 2, mixing speed is 150~180r/min.
9. the preparation method of alpha-semi water plaster stone/hydroxyapatite composite microspheres according to claim 1, it is characterised in that：
Wherein, in step 3, drying condition is：Dry 2~4h under the conditions of 45~60 DEG C.
10. a kind of alpha-semi water plaster stone/hydroxyapatite composite microspheres, it is characterised in that：
Using the preparation method system of alpha-semi water plaster stone/hydroxyapatite composite microspheres described in any one of claim 1 to 9
.
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| CN114591060A (en) * | 2022-04-28 | 2022-06-07 | 西北大学 | Gypsum-basic calcium phosphate three-dimensional interpenetrating material and preparation method thereof |
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