CN102488920B - Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof - Google Patents
Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof Download PDFInfo
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- CN102488920B CN102488920B CN 201110416270 CN201110416270A CN102488920B CN 102488920 B CN102488920 B CN 102488920B CN 201110416270 CN201110416270 CN 201110416270 CN 201110416270 A CN201110416270 A CN 201110416270A CN 102488920 B CN102488920 B CN 102488920B
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- hydroxyapatite
- calcium sulphate
- crystal modifier
- deionized water
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 51
- 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 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title abstract description 8
- 239000008187 granular material Substances 0.000 title abstract description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 20
- 235000011132 calcium sulphate Nutrition 0.000 claims description 49
- 239000001175 calcium sulphate Substances 0.000 claims description 39
- 239000011246 composite particle Substances 0.000 claims description 24
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 229940103272 aluminum potassium sulfate Drugs 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 6
- 238000002347 injection Methods 0.000 abstract description 3
- 239000007924 injection Substances 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000007596 consolidation process Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 description 17
- 210000000988 bone and bone Anatomy 0.000 description 12
- 239000001506 calcium phosphate Substances 0.000 description 10
- 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 description 9
- 229910000389 calcium phosphate Inorganic materials 0.000 description 8
- 235000011010 calcium phosphates Nutrition 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002639 bone cement Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 239000000316 bone substitute Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002324 minimally invasive surgery Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
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Abstract
The invention discloses an alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with a nuclear shell structure and preparation thereof. The composite granule has a microstructure in which the hydroxyapatite wraps the alpha-calcium sulfate hemihydrate. The preparation method comprises the steps of: using deionized water as a solvent, dissolving a proper dosage of organic crystal modifier and inorganic salt crystal modifier, adding calcium sulfate dehydrate and hydroxyapatite, and performing hydrothermal synthesis under certain technical parameters. According to the invention, the alpha-calcium sulfate hemihydrate and the hydroxyapatite are compounded in the microstructure so as to adjust the quick consolidation defect of pure alpha-calcium sulfate hemihydrate to improve the injection performance thereof, and a microstructure with a controllable wrapping degree can be formed to adjust and control the biodegradation performance thereof, so that the composite granule has a brilliant clinical application prospect.
Description
Technical field
The invention belongs to the bio-medical material preparing technical field, be specifically related to a kind of α-half-H 2 O calcium sulphate of nucleocapsid structure/hydroxyapatite composite particles and preparation method thereof.
Background technology
Calcium sulfate (CS) is applied to clinical existing more than 100 year history as bone grafting material, and its safety in human body is confirmed by numerous experiment already.It is good that calcium sulfate has histocompatibility, and the slightly acidic environment and the calcium phosphate crystal that form after bone-inducting active height, the biodegradation can attract osteoclast, accelerate the characteristics such as new bone formation.But calcium sulfate degradation in vivo excessive velocities becomes a factor that limits its clinical practice.
The medical calcium sulfate bone substitute OsteoSet that U.S. Wright Healtech S.A. develops in succession and MIIG series is all take the α-half-H 2 O calcium sulphate of given shape and size as the basis.This medical grade calcium sulfate has stable 3-d modelling, so that newly bone can be reinvented by this configuration, and quality, intensity and the profile of new bone and normal bone is matched.Its purity is high, impurity is few, and the crystal structure height is consistent, and its absorption rate is stable after implanting, but the relative new bone growth speed of its absorption rate is still very fast.
Studying at present and use the more calcium phosphate as bioactive materials is hydroxyapatite and tricalcium phosphate.Wherein, hydroxyapatite has similar chemical constituent, crystal structure to osseous tissue, is easy to be utilized by host bone, and degraded slowly has good bone conduction effect.The syringeability calcium phosphate bone cement claims again the self-curing bone cement, and is easy and simple to handle, and good biocompatibility can be injected to the marrow damaged place, and in-situ solidifying adapts to that bone is damaged to carry out mouldingly, meets the requirement of minimally invasive surgery, has become various countries scholar's a study hotspot.But its degraded slowly usually, and retention time is long in vivo, does not reach requirement degradable within the treatment phase, has affected growing into of new bone, and extensive use is subject to restriction to a certain degree.
Too fast for the calcium sulfate absorption rate, problem is studied and is reported also much and calcium phosphate is degraded slowly, and purpose all is the advantage in conjunction with both, prepares the composite with good biological performance.The patent No. is that the Chinese invention patent of ZL200710063903.4 discloses a kind of new-type of inorganic bone grafting material, is comprised of by certain mass fraction proportioning bata-tricalcium phosphate and α-half-H 2 O calcium sulphate; Application number is the preparation method that 201010201897.6 Chinese invention patent application discloses a kind of self pore-forming calcium phosphate cement bracket, and certain calcium sulfate is joined the injectable calcium phosphate bone cement, prepares novel composite bone cement; Application number is that 201010185090.8 Chinese invention patent application discloses a kind of Composite Bone based on nanometer hydroxyapatite and half-H 2 O calcium sulphate and repairs material and preparation method thereof, and α-half-H 2 O calcium sulphate, hydroxyapatite and additive are formed composite bone repairing material.But just simple mixing of calcium sulfate and calcium phosphate in its microstructure, its dissolving and degradation behavior characteristic are still followed the characteristics of calcium sulfate and calcium phosphate self, do not obtain good regulation and control.
Summary of the invention
The invention provides a kind of α-half-H 2 O calcium sulphate of nucleocapsid structure/hydroxyapatite composite particles and preparation method thereof, realize compound in microstructure of α-half-H 2 O calcium sulphate/hydroxyapatite, to adjust the fast setting of simple α-half-H 2 O calcium sulphate, improve its injection property, and according to the difference of wrapping up degree in the microstructure, can regulate and control its biodegradability.
A kind of α-half-H 2 O calcium sulphate of nucleocapsid structure/hydroxyapatite composite particles has the microstructure that hydroxyapatite wraps up α-half-H 2 O calcium sulphate, and described α-half-H 2 O calcium sulphate is generally cylindric or six side's α-half-H 2 O calcium sulphates.
α-the half-H 2 O calcium sulphate of described nucleocapsid structure/hydroxyapatite composite particles is prepared by following methods:
(1) adding organic crystal modifier and inorganic salts crystal modifier in deionized water are stirred to fully dissolving, make to turn brilliant solution; Wherein, described organic crystal modifier is sodium citrate, citric acid, succinic acid or potassium oxalate, and described inorganic salts crystal modifier is magnesium sulfate, aluminum sulfate or potassium sulfate; The quality of described organic crystal modifier is 0.05%～0.2% of described deionized water quality, and the quality of described inorganic salts crystal modifier is 0.5%～2% of described deionized water quality;
(2) add successively calcium sulphate dihydrate and hydroxyapatite in the brilliant solution to described turning, form solid-liquid mixing system; Wherein, the mass ratio of described calcium sulphate dihydrate and described deionized water is 1: (2～6), and described hydroxyapatite: the mass ratio of calcium sulphate dihydrate is (0.1～1): 1;
(3) described solid-liquid mixing system is placed 130～160 ℃ water heating kettle constant temperature process after 4～8 hours, from described water heating kettle, leach crude product;
(4) water of described crude product with 90～100 ℃ is cleaned, again 90～110 ℃ of dryings, obtain α-half-H 2 O calcium sulphate/hydroxyapatite composite particles.
In the preferred technical scheme, the quality of described organic crystal modifier is 0.05% of described deionized water quality, and the quality of described inorganic salts crystal modifier is 2% of described deionized water quality.
In the preferred technical scheme, the mass ratio of described calcium sulphate dihydrate and described deionized water is 1: 4, described hydroxyapatite: the mass ratio of calcium sulphate dihydrate is 0.75: 1.
Among the present invention, take deionized water as solvent, be dissolved into an amount of organic crystal modifier and inorganic salts crystal modifier, add sulfate dihydrate calcium powder and hydroxyapatite, and the method by Hydrothermal Synthesis prepares α-half-H 2 O calcium sulphate with nucleocapsid structure/hydroxyapatite composite particles under certain technological parameter, and this composite particles has the microstructure of hydroxyapatite parcel α-half-H 2 O calcium sulphate.
The present invention by the method for hydrothermal treatment consists, dissolves and recrystallization the sulfate dihydrate calcium powder by introduce organic carboxyl acid root and inorganic ion in aqueous medium under certain pressure and temperature, be transformed into α-half-H 2 O calcium sulphate, and particle size is 5～30 μ m; Simultaneously, because the existence of additive hydroxyapatite, it forms clad on α-half-H 2 O calcium sulphate surface, affects the hydration characteristics of α-half-H 2 O calcium sulphate, improves its injection property; And along with the difference of both ratios, the coating degree of microstructure is different, when affect its hydration characteristics, and the degradation property when also affecting its clinical practice, thus realization is to the regulation and control of biodegradability.
Compared with prior art, the present invention has following useful technique effect:
Composite particles of the present invention has been realized compound in microstructure of α-half-H 2 O calcium sulphate/hydroxyapatite, be wrapped in the hydroxyapatite on α-half-H 2 O calcium sulphate surface because dissolution characteristics is fully different from α-half-H 2 O calcium sulphate, played the effect of regulation and control surface with the water reaction rate, thereby can effectively adjust the granule degradation characteristic, have preferably potential applicability in clinical practice.Preparation method of the present invention is simple, and is simple to operate, and cost is low, is easy to industrialization.
Description of drawings
Fig. 1 is the XRD figure of the composite particles for preparing of embodiment 1.
Fig. 2 is the microscopic appearance figure of the composite particles for preparing of embodiment 1.
Fig. 3 be the composite particles centre position for preparing of embodiment 1 can spectrogram.
Fig. 4 be the composite particles edge for preparing of embodiment 1 can spectrogram.
Fig. 5 is the XRD figure of the composite particles for preparing of embodiment 2.
Fig. 6 is the microscopic appearance figure of the composite particles for preparing of embodiment 2.
The specific embodiment
Describe the present invention in detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to this.
Embodiment 1
Get the deionized water of 40ml as solvent, the sodium citrate and the mass fraction that add 0.02g are the magnesium sulfate of 0.8g, are stirred to fully dissolving, make to turn brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add again the hydroxyapatite of 7.5g, form solid-liquid mixing system.
To join solid-liquid mixing system place 130 ℃ water heating kettle constant temperature to process 6 hours, exit after the hydrothermal treatment consists, fast fetching goes out water heating kettle, and from water heating kettle, leach crude product, clean in the baking oven that is placed on 90 ℃ with 90 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.
Adopt X-ray diffractometer that the end product of gained is carried out component analysis and component sign, XRD figure is composed as shown in Figure 1.Among Fig. 1, curve a and b are respectively the standard spectrogram of α-half-H 2 O calcium sulphate (CSH) and hydroxyapatite (HA), and curve c composes corresponding to the XRD figure of end product, as seen, ● locate peak position and belong to α-half-H 2 O calcium sulphate, zero place's peak position belongs to hydroxyapatite.Fig. 1 shows that the end product of present embodiment preparation is α-half-H 2 O calcium sulphate/hydroxyapatite composite particles.
The employing scanning electron microscope is carried out the microscopic appearance sign to the end product of gained, and SEM schemes as shown in Figure 2, and as seen, end product has nucleocapsid structure, on columned α-half-H 2 O calcium sulphate surface clad is arranged.
By the energy spectrum analysis to end product granule centre position (corresponding to (1) among Fig. 2) and edge (corresponding to (2) among Fig. 2) of gained, respectively as shown in Figure 3 and Figure 4, as seen the P constituent content on top layer is higher than inside, shows that clad is hydroxyapatite.
Embodiment 2
Get the deionized water of 40ml as solvent, the succinic acid of adding 0.04g and the aluminum sulfate of 0.6g are stirred to fully dissolving, make to turn brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add again the hydroxyapatite of 5g, form solid-liquid mixing system.
To join solid-liquid mixing system place 160 ℃ water heating kettle constant temperature to process 4 hours, exit after the hydrothermal treatment consists, fast fetching goes out water heating kettle, and from water heating kettle, leach crude product, clean in the baking oven that is placed on 110 ℃ with 95 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.
Adopt X-ray diffractometer that the end product of gained is carried out component analysis and component sign, XRD figure is composed as shown in Figure 5.Among Fig. 5, curve a and b are respectively the standard spectrogram of α-half-H 2 O calcium sulphate (CSH) and hydroxyapatite (HA), and curve d composes corresponding to the XRD figure of end product, as seen, ● locate peak position and belong to α-half-H 2 O calcium sulphate, zero place's peak position belongs to hydroxyapatite.Fig. 5 shows that the end product of present embodiment preparation is α-half-H 2 O calcium sulphate/hydroxyapatite composite particles.
The employing scanning electron microscope is carried out the microscopic appearance sign to the end product of gained, SEM schemes as shown in Figure 6, and particle surface has more covering to exist, and visible end product has nucleocapsid structure, further the particle surface clad is carried out energy spectrum analysis, show that clad is hydroxyapatite.
Embodiment 3
Get the deionized water of 40ml as solvent, the citric acid of adding 0.08g and the magnesium sulfate of 0.2g are stirred to fully dissolving, make to turn brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add again the hydroxyapatite of 2.5g, form solid-liquid mixing system.
To join solid-liquid mixing system place 140 ℃ water heating kettle constant temperature to process 8 hours, exit after the hydrothermal treatment consists, fast fetching goes out water heating kettle, and from water heating kettle, leach crude product, clean in the baking oven that is placed on 90 ℃ with 100 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.Through characterizing, end product is the α-half-H 2 O calcium sulphate/hydroxyapatite composite particles of nucleocapsid structure.
Embodiment 4
Get the deionized water of 40ml as solvent, the potassium oxalate of adding 0.06g and the potassium sulfate of 0.4g are stirred to fully dissolving, make to turn brilliant solution; To wherein adding 10g sulfate dihydrate calcium powder (analytical pure level), add again the hydroxyapatite of 10g, form solid-liquid mixing system.
To join solid-liquid mixing system place 150 ℃ water heating kettle constant temperature to process 6 hours, exit after the hydrothermal treatment consists, fast fetching goes out water heating kettle, and from water heating kettle, leach crude product, clean in the baking oven that is placed on 100 ℃ with 95 ℃ hot water sucking filtration and to dry, obtain end product, be graininess.Through characterizing, end product is α-half-H 2 O calcium sulphate with nucleocapsid structure/hydroxyapatite composite particles.
Claims (3)
1. the preparation method of the α-half-H 2 O calcium sulphate of a nucleocapsid structure/hydroxyapatite composite particles is characterized in that, may further comprise the steps:
(1) adding organic crystal modifier and inorganic salts crystal modifier in deionized water are stirred to fully dissolving, make to turn brilliant solution; Wherein, described organic crystal modifier is sodium citrate, citric acid, succinic acid or potassium oxalate, and described inorganic salts crystal modifier is magnesium sulfate, aluminum sulfate or potassium sulfate; The quality of described organic crystal modifier is 0.05%～0.2% of described deionized water quality, and the quality of described inorganic salts crystal modifier is 0.5%～2% of described deionized water quality;
(2) add successively calcium sulphate dihydrate and hydroxyapatite in the brilliant solution to described turning, form solid-liquid mixing system; Wherein, the mass ratio of described calcium sulphate dihydrate and described deionized water is 1:(2～6), described hydroxyapatite: the mass ratio of calcium sulphate dihydrate is (0.1～1): 1;
(3) described solid-liquid mixing system is placed 130～160 ℃ water heating kettle constant temperature process after 4～8 hours, from described water heating kettle, leach crude product;
(4) water of described crude product with 90～100 ℃ is cleaned, again 90～110 ℃ of dryings, obtain α-half-H 2 O calcium sulphate/hydroxyapatite composite particles; Wherein, described α-half-H 2 O calcium sulphate/hydroxyapatite composite particles has the microstructure of hydroxyapatite parcel α-half-H 2 O calcium sulphate.
2. the preparation method of the α-half-H 2 O calcium sulphate of nucleocapsid structure as claimed in claim 1/hydroxyapatite composite particles, it is characterized in that, the quality of described organic crystal modifier is 0.05% of described deionized water quality, the quality of described inorganic salts crystal modifier be described deionized water quality 2%.
3. the preparation method of the α-half-H 2 O calcium sulphate of nucleocapsid structure as claimed in claim 1/hydroxyapatite composite particles, it is characterized in that, the mass ratio of described calcium sulphate dihydrate and described deionized water is 1:4, described hydroxyapatite: the mass ratio of calcium sulphate dihydrate is 0.75:1.
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| CN102815682A (en) * | 2012-09-07 | 2012-12-12 | 浙江大学 | Biomedical beta-Ca(HPO4)*(SO4)1-*.1/2H2O solid solution particle and preparation method thereof |
| CN102815683B (en) * | 2012-09-07 | 2014-06-25 | 浙江大学 | Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof |
| CN103251976B (en) * | 2013-05-06 | 2015-01-14 | 浙江大学 | Biomedical calcium sulfate based composite particle for slowly releasing metal ions and preparation method of biomedical calcium sulfate based composite particle |
| CN105107023A (en) * | 2015-07-01 | 2015-12-02 | 李亚屏 | Degradable porous composite scaffold material for bone transplantation |
| CN108525004B (en) * | 2018-05-09 | 2020-11-17 | 湖北民族学院 | Alpha-hemihydrate gypsum/hydroxyapatite composite microsphere and preparation method thereof |
| CN109224125A (en) * | 2018-09-28 | 2019-01-18 | 福州大学 | A kind of syringeability shell/calcium sulfate bone cement and preparation method thereof |
| CN109793922A (en) * | 2019-03-01 | 2019-05-24 | 昆明理工大学 | A kind of calcium sulphate dihydrate/monetite Core-shell structure material and preparation method thereof |
| CN109821066A (en) * | 2019-03-04 | 2019-05-31 | 昆明理工大学 | A kind of preparation method of gelatin/dicalcium phosphate dihydrate/calcium sulphate dihydrate porous support |
| CN114477261A (en) * | 2020-10-26 | 2022-05-13 | 北京威达峰医学生物材料有限责任公司 | Preparation method of high-purity surgical grade alpha-calcium sulfate hemihydrate with adjustable crystal size |
| CN114522276B (en) * | 2022-03-04 | 2023-03-17 | 武汉理工大学 | Zinc-doped semi-hydrated calcium sulfate based composite artificial bone material and preparation method and application thereof |
| CN115414525B (en) * | 2022-09-26 | 2023-08-18 | 杭州归领医疗器械有限公司 | Medical calcium sulfate artificial bone powder with core-shell structure and preparation method thereof |
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| CN101843918A (en) * | 2010-05-27 | 2010-09-29 | 甘少磊 | Composite bone repairing material based on nano-hydroxyapatite and hemihydrate calcium sulfate and preparation method thereof |
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