CN118320175A - Preparation and application of rare earth doped nano hydroxyapatite/zirconium dioxide composite material - Google Patents
Preparation and application of rare earth doped nano hydroxyapatite/zirconium dioxide composite material Download PDFInfo
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- CN118320175A CN118320175A CN202410441583.5A CN202410441583A CN118320175A CN 118320175 A CN118320175 A CN 118320175A CN 202410441583 A CN202410441583 A CN 202410441583A CN 118320175 A CN118320175 A CN 118320175A
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 120
- 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 109
- 239000002131 composite material Substances 0.000 title claims abstract description 105
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 92
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 26
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000013078 crystal Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 25
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 12
- 230000008439 repair process Effects 0.000 claims abstract description 11
- 230000017423 tissue regeneration Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 77
- 230000033558 biomineral tissue development Effects 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 23
- 238000011065 in-situ storage Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 14
- 108010022355 Fibroins Proteins 0.000 claims description 14
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 14
- 238000004381 surface treatment Methods 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 11
- 159000000007 calcium salts Chemical class 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000001089 mineralizing effect Effects 0.000 claims description 6
- -1 rare earth salt Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 38
- 229910052727 yttrium Inorganic materials 0.000 description 25
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000012153 distilled water Substances 0.000 description 16
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 15
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 15
- 235000019837 monoammonium phosphate Nutrition 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- 229910001424 calcium ion Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 235000015895 biscuits Nutrition 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000006012 monoammonium phosphate Substances 0.000 description 3
- 229910002976 CaZrO3 Inorganic materials 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 239000010839 body fluid Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Materials For Medical Uses (AREA)
Abstract
The invention discloses preparation and application of a rare earth doped nano hydroxyapatite/zirconium dioxide composite material, and relates to the technical field of bone repair materials. The tetragonal crystal zirconium dioxide/hydroxyapatite composite material is prepared from zirconium dioxide and rare earth doped nano hydroxyapatite as raw materials, is a novel composite material, has biocompatibility and antibacterial property, has higher toughness and higher rigidity, can be used as an excellent bone repair material and an excellent oral hard tissue repair material, and also has wide application prospect in related fields due to the excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of bone repair materials, in particular to preparation and application of a rare earth doped nano hydroxyapatite/zirconium dioxide composite material.
Background
The zirconium dioxide ceramic material has smooth surface, has the color similar to that of bones, is not easy to yellow, has good biocompatibility, is not easy to corrode in body fluid environment, can meet the requirements on aesthetic feeling of the material and practicality, and is favored in the fields of hard tissues and bone repair of oral cavities.
Zirconium dioxide has higher hardness and good compressive strength, but zirconium dioxide in different crystal forms has great difference in expansibility, zirconium dioxide can be converted from monoclinic to tetragonal at 1100-1200 ℃ to cause obvious volume shrinkage, and when the temperature is reduced, the crystal forms are converted to cause volume expansion to cause cracking of ceramic, so that certain oxides are needed to be added to fill gaps in crystal lattices to inhibit conversion of the crystal forms of zirconium dioxide and realize phase change toughening. Traditionally added oxides are mainly yttria and alumina. The yttrium oxide is used as the stabilizer, so that the service life of the composite material is reduced, and the strength and stability are greatly reduced under the condition of long-term load; the use of alumina as a stabilizer, while having a good life, leads to a general decrease in the mechanical properties of the composite due to its greater porosity.
The novel zirconia bone repair and oral hard tissue repair material with good biocompatibility and stable property is provided, and has important positive significance.
Disclosure of Invention
The invention aims to provide preparation and application of a rare earth doped nano hydroxyapatite/zirconium dioxide composite material, so as to solve the problems in the prior art and further meet the performance requirements of bone repair and oral hard tissue repair materials.
In order to achieve the above object, the present invention provides the following solutions:
The invention provides a preparation method of a tetragonal crystal form zirconium dioxide/hydroxyapatite composite material (rare earth doped nano hydroxyapatite/zirconium dioxide composite material), which comprises the following steps:
(1) Preparation of rare earth doped nano hydroxyapatite
Adding calcium salt and rare earth salt into the solution, mixing, adding phosphate ion solution for reaction, controlling the molar ratio of the calcium to the rare earth in the reaction system to be (1.57-1.62) (0.05-0.10), controlling the molar ratio of the total calcium to the rare earth to the phosphorus to be 1.67, carrying out heat preservation and mineralization on the obtained reaction solution, carrying out suction filtration, washing and freeze drying to obtain the rare earth doped nano hydroxyapatite;
the temperature of the heat preservation and mineralization is 20-25 ℃, the time is 24-36h, and the pressure is 0.1MPa;
(2) Preparation of tetragonal crystal form zirconium dioxide/hydroxyapatite composite material:
Mixing zirconium dioxide and the rare earth doped nano hydroxyapatite, and sintering to obtain the tetragonal crystal zirconium dioxide/hydroxyapatite composite material.
As a further preferred aspect of the present invention, the temperature of the reaction in step (1) is 37℃and the pH is 9 to 10; the sintering temperature in the step (2) is 1100-1200 ℃ and the sintering time is 3-4h.
In the invention, the mass ratio of the rare earth doped nano hydroxyapatite to the zirconium dioxide is 1:1, 1:2 or 1:5.
As a further preferred aspect of the present invention, the reaction in step (1) is carried out at a temperature of 37℃and a pH of 9 to 10.
As a further preferred aspect of the present invention, the pH value of the system is adjusted by using ammonia water in the step (1); more preferably, the mass concentration of ammonia water is 25%.
As a further preferred aspect of the present invention, the calcium salt in step (1) is calcium nitrate; the rare earth salt is yttrium chloride hexahydrate; the phosphate ion salt is monoammonium phosphate.
As a further preferred aspect of the present invention, the freeze-drying temperature in step (1) is-80℃and the freeze-drying time is 72 hours.
As a further preferred aspect of the present invention, the sintering temperature in step (2) is 1100-1200 ℃ and the time is 3-4 hours.
As a further preferred aspect of the present invention, in the step (2), a step of tabletting is further included before sintering; preferably, the tabletting pressure is 15MPa, and the tabletting time is 1min.
As a further preferred aspect of the present invention, after the step (2) of the preparation method, the method further comprises a step of performing in-situ mineralization treatment: and immersing the tetragonal crystal zirconium dioxide/hydroxyapatite composite material in a calcium salt solution, mineralizing in a phosphate radical solution, and sintering to obtain the tetragonal crystal zirconium dioxide/hydroxyapatite composite material.
As a further preferred aspect of the present invention, after the step (2) of the preparation method, the method further comprises a step of performing in-situ mineralization after performing surface treatment with a silk fibroin solution:
Coating a silk fibroin solution on the surface of the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material for surface treatment, soaking the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material subjected to surface treatment in a calcium salt solution, mineralizing in a phosphate radical solution, and sintering to obtain the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material.
As a further preferred aspect of the present invention, the method for preparing a silk fibroin solution comprises the steps of:
Adding the colloid-removed silk into a mixed solution of NaOH and CO (NH 2)2), and treating at 60 ℃ for 3 hours to obtain the silk fibroin solution.
More preferably, the molar concentration ratio of NaOH and CO (NH 2)2) in the mixed solution of NaOH and CO (NH 2)2 is 1.2:8.
The more preferred preparation steps of the silk fibroin solution are as follows:
Adding the crushed silk into 0.2-0.5 mol/L NaHCO 3 solution, heating and boiling for 0.5h to remove colloid in the silk, taking out, washing twice with distilled water until neutral, drying in an oven at 80 ℃ for 2h, and taking out for later use. Respectively weighing 4.8g of NaOH and 7.2gCO g of distilled water (NH 2)2 is mixed with 100mL of distilled water to prepare NaOH and CO (NH 2)2) solution with the molar concentration of 1.2:8, putting degummed silk into the solution, heating to 60 ℃, preserving heat for 3h, and dialyzing the clear solution through a filter membrane to obtain a silk fibroin solution.
As a further preferred aspect of the present invention, after the step (2) of the preparation method, the method further includes a step of performing in-situ mineralization after performing surface treatment with a dopamine hydrochloride solution:
Soaking the surface of the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material in a dopamine hydrochloride solution for surface treatment, soaking the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material subjected to surface treatment in a calcium salt solution, mineralizing in a phosphate radical solution, and sintering to obtain the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material.
As a further preferred aspect of the present invention, the concentration of the dopamine hydrochloride solution is 2mg/mL, the soaking temperature is 37 ℃, and the soaking time is 24 hours.
The dopamine hydrochloride solution can be prepared by the following steps: 10mL of 50mM Tris HCl solution is measured in a 50mL volumetric flask, water is added to fix the volume, and 0.1238g of dopamine hydrochloride is accurately weighed and dissolved in the prepared Tris HCl solution.
As a further preferred aspect of the invention, the sintering treatment temperature of in situ mineralization is 400-500 ℃ and the time is 2-3h.
As a further preferred aspect of the invention, the concentration of the calcium salt solution is 32.5% during the in situ mineralization treatment, the soaking temperature is 37 ℃ and the soaking time is 10-12h. More preferably, in the in-situ mineralization treatment process, when the calcium salt solution is soaked, ammonia water is used for adjusting the pH value to 9-10, and the calcium ion film is obtained on the surface of the material.
As a further preferred aspect of the invention, the mineralization time in the phosphate solution is 24 hours.
The invention also provides the tetragonal crystal zirconium dioxide/hydroxyapatite composite material prepared by the preparation method.
The invention further provides application of the tetragonal zirconium dioxide/hydroxyapatite composite material as a bone repair material or an oral hard tissue repair material.
The tetragonal zirconium dioxide material has stronger bearing capacity, better toughness and higher rigidity, but can only exist stably at high temperature. The invention carries out high-temperature sintering on rare earth doped hydroxyapatite and zirconium dioxide without using an adhesive, thereby realizing the transformation of zirconium dioxide from monoclinic type to tetragonal type. Hydroxyapatite is one of the main inorganic components of bone, but has high brittleness and does not have excellent compressive strength, so that it cannot be used alone as a bone repair material. Zirconium ions and calcium ions have similar radii and properties, and hydroxyapatite can be decomposed into Ca 3(PO4)2、CaO、CaZrO3 and the like in the high-temperature calcination process, so that the gaps of zirconium dioxide crystal lattices can be compensated, and the tetragonal nano hydroxyapatite/zirconium dioxide composite material which exists stably at normal temperature can be obtained.
Meanwhile, ca 3(PO4)2、CaO、CaZrO3 and the like obtained by decomposing the hydroxyapatite in the high-temperature calcination process have good biocompatibility, and part of the hydroxyapatite can be degraded in a body fluid environment, so that phosphorus and calcium elements necessary for a human body are released, and are absorbed by human tissue cells for reuse to promote cell growth. Meanwhile, calcium ions and partial rare earth ions have similar radiuses, and can be doped with the rare earth ions in the reaction process, so that the hydroxyapatite has certain antibacterial capacity.
The invention utilizes the calcium ion solution to carry out in-situ mineralization on the composite material obtained by sintering the rare earth doped nano hydroxyapatite and zirconium dioxide, generates the hydroxyapatite film by in-situ mineralization on the activation site of the crystal, can weaken the interface acting force between the crystals, and ensures firm connection with the surface of the repair material without falling off.
The tetragonal crystal form zirconium dioxide/hydroxyapatite composite material has high biocompatibility and toughness, and can be reused. When the tetragonal crystal zirconium dioxide/hydroxyapatite composite material is used as the liner, the tetragonal crystal zirconium dioxide/hydroxyapatite composite material can be subjected to repeated mineralization treatment, so that the tetragonal crystal zirconium dioxide/hydroxyapatite composite material can be repeatedly connected with a shell on the basis of in-situ mineralization to generate the hydroxyapatite shell, and the repeated use performance is ensured.
The hydroxyapatite film is generated on the surface of the composite material by in-situ mineralization, so that the biocompatibility of the composite material is further improved, the internal abrasion is reduced, and the effect of repeated use is achieved.
The technical scheme of the invention can effectively solve the problem that the hydroxyapatite material has low strength and toughness and does not have antibacterial capability so as to limit clinical use.
The invention discloses the following technical effects:
The tetragonal crystal zirconium dioxide/hydroxyapatite composite material is prepared from zirconium dioxide and rare earth doped nano hydroxyapatite as raw materials, is a novel composite material, has biocompatibility and antibacterial property, has higher toughness and higher rigidity, can be used as an excellent bone repair material and an excellent oral hard tissue repair material, and also has wide application prospect in related fields due to the excellent comprehensive performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a transmission electron microscope image of yttrium-doped nano-hydroxyapatite material prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of yttrium-doped nano-hydroxyapatite/zirconium dioxide composite material prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern for a composite material before in situ mineralization and after in situ mineralization in example 2 of the present invention;
FIG. 4 is a graph showing the antibacterial properties of the nano-hydroxyapatite/zirconia composite material coated with the hydroxyapatite film prepared in example 2 and example 3 according to the present invention;
FIG. 5 is a scanning electron microscope image of a nano-hydroxyapatite/zirconia composite material coated with a hydroxyapatite film prepared in example 4 of the present invention;
FIG. 6 is a scanning electron microscope image of a nano-hydroxyapatite/zirconia composite material coated with a hydroxyapatite film prepared in example 5 of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples of the present invention are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
EXAMPLE 1 preparation of tetragonal zirconium dioxide/hydroxyapatite composite
(1) Preparation of rare earth doped nano hydroxyapatite
5.18G of calcium nitrate and 0.297g of yttrium chloride hexahydrate are weighed and dissolved in 100mL of distilled water, and a solution of calcium nitrate containing yttrium with the molar ratio of calcium to yttrium being 1.62:0.05 is prepared, and then 2.24g of ammonium dihydrogen phosphate is weighed and dissolved in 100mL of distilled water. Dropping the ammonium dihydrogen phosphate solution into the yttrium-containing calcium nitrate solution, maintaining the pH value of the reaction system at 9-10 by using 25% ammonia water by mass fraction, magnetically stirring at 300r/min for 12h, and aging for 24h under the conditions of 0.1MPa and 25 ℃. And (3) carrying out suction filtration, and freeze-drying the solid at the temperature of-80 ℃ for 72 hours to obtain the yttrium-doped nano-hydroxyapatite.
(2) Preparation of composite materials
Mixing yttrium-doped nano hydroxyapatite with zirconium dioxide powder according to a mass ratio of 1:1, tabletting under the condition of the pressure of 15MPa and room temperature, and sintering the obtained white biscuit at 1200 ℃ for 3 hours to obtain the composite material. (tetragonal crystal form zirconium dioxide/hydroxyapatite composite material).
The transmission electron microscope photograph of the yttrium-doped nano-hydroxyapatite prepared in the example is shown in fig. 1. Yttrium doping was successful and is nano-scale hydroxyapatite.
The transmission electron microscope photograph of the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material prepared in the embodiment is shown in figure 2. The presence of tetragonal zirconium dioxide can be clearly seen.
EXAMPLE 2 preparation of tetragonal zirconium dioxide/hydroxyapatite composite
(1) Preparation of rare earth doped nano hydroxyapatite
5.18G of calcium nitrate and 0.297g of yttrium chloride hexahydrate are weighed and dissolved in 100mL of distilled water, and a solution of calcium nitrate containing yttrium with the molar ratio of calcium to yttrium being 1.62:0.05 is prepared, and then 2.24g of ammonium dihydrogen phosphate is weighed and dissolved in 100mL of distilled water. Dropping the ammonium dihydrogen phosphate solution into the yttrium-containing calcium nitrate solution, maintaining the pH value of the reaction system at 9-10 by using 25% ammonia water by mass fraction, magnetically stirring at 300r/min for 12h, and aging for 24h under the conditions of 0.1MPa and 25 ℃. And (3) carrying out suction filtration, and freeze-drying the solid at the temperature of-80 ℃ for 72 hours to obtain the yttrium-doped nano-hydroxyapatite.
(2) Preparation of composite materials
Mixing yttrium-doped nano hydroxyapatite with zirconium dioxide powder according to a mass ratio of 1:1, tabletting under the condition of a pressure of 15MPa and a room temperature, and sintering the obtained white biscuit at 1200 ℃ for 3 hours to obtain the composite material (tetragonal crystal zirconium dioxide/hydroxyapatite composite material).
(3) In situ mineralization
The surface of the obtained composite material is washed and cleaned by deionized water and absolute ethyl alcohol in sequence and is treated by ultrasonic for 10 minutes, the material is immersed into calcium nitrate solution with the concentration of 32.5 percent, ammonia water is added to regulate the pH value, the pH value is maintained at 9-10, the composite material coated with a calcium ion film is obtained, the composite material is then put into monoammonium phosphate solution with the concentration of 19.5 percent to be mineralized for 24 hours, and then the composite material is sintered for 3 hours at 400 ℃, washed and dried, and the yttrium doped hydroxyapatite/zirconium dioxide composite material with the surface coated by a hydroxyapatite film is obtained.
Fig. 3 is an XRD pattern of the composite material before and after in-situ mineralization in this example. Wherein B is an unmineralized composite material; c is a mineralized composite material; d is a composite material subjected to grinding treatment after mineralization, the peak value of B is the largest, and the peak value of D is larger than that of C, so that the successful mineralization of the hydroxyapatite on the surface of the composite material can be preliminarily illustrated.
EXAMPLE 3 preparation of tetragonal zirconium dioxide/hydroxyapatite composite
(1) Preparation of rare earth doped nano hydroxyapatite
5.03G of calcium nitrate and 0.593g of yttrium chloride hexahydrate are weighed and dissolved in 100mL of distilled water, a calcium nitrate solution containing yttrium with the molar ratio of calcium to yttrium being 1.57:0.10 is prepared, and 2.24g of ammonium dihydrogen phosphate is weighed and dissolved in 100mL of distilled water. Dropping the ammonium dihydrogen phosphate solution into the yttrium-containing calcium nitrate solution, maintaining the pH value of the reaction system at 9-10 by using 25% ammonia water by mass fraction, magnetically stirring at 300r/min for 12h, and aging for 24h under the conditions of 0.1MPa and 25 ℃. And (3) carrying out suction filtration, and freeze-drying the solid at the temperature of-80 ℃ for 72 hours to obtain the yttrium-doped nano-hydroxyapatite.
(2) Preparation of composite materials
Mixing yttrium-doped nano hydroxyapatite with zirconium dioxide powder according to a mass ratio of 1:1, tabletting under the condition of a pressure of 15MPa and a room temperature, and sintering the obtained white biscuit at 1200 ℃ for 3 hours to obtain the composite material (tetragonal crystal zirconium dioxide/hydroxyapatite composite material).
(3) In situ mineralization
The surface of the obtained composite material is washed and cleaned by deionized water and absolute ethyl alcohol in sequence and is treated by ultrasonic for 10 minutes, the material is immersed into calcium nitrate solution with the concentration of 32.5 percent, ammonia water is added to regulate the pH value, the pH value is maintained at 9-10, the composite material coated with a calcium ion film is obtained, the composite material is then put into monoammonium phosphate solution with the concentration of 19.5 percent to be mineralized for 24 hours, and then the composite material is sintered for 3 hours at 400 ℃, washed and dried, and the yttrium doped hydroxyapatite/zirconium dioxide composite material with the surface coated by a hydroxyapatite film is obtained.
The antibacterial performance of the nano hydroxyapatite/zirconium dioxide composite material with the surface wrapped by the hydroxyapatite film prepared in the embodiment 2 and the embodiment 3 is shown in fig. 4 and table 1, and under the condition that other conditions are the same, the inhibition condition of the composite material doped with yttrium with different content on escherichia coli in 24 hours is observed after sterilization treatment, so that the antibacterial performance is influenced by the yttrium doped content, namely the larger the yttrium content is, the larger the inhibition effect on escherichia coli is.
TABLE 1
| Sample of | Yttrium content/% | Radius/mm of inhibition zone |
| 1 | 0 | 6 |
| 2 | 3 | 9 |
| 3 | 6 | 11 |
In table 1, sample 1 is a blank control, sample 2 is a nano hydroxyapatite/zirconia composite material with a surface coated with a hydroxyapatite film prepared in example 2, and sample 3 is a nano hydroxyapatite/zirconia composite material with a surface coated with a hydroxyapatite film prepared in example 3. Samples 1,2, 3 in table 1 correspond to numbers 0, 3, 6 in fig. 4, respectively.
EXAMPLE 4 preparation of tetragonal zirconium dioxide/hydroxyapatite composite
(1) Preparation of rare earth doped nano hydroxyapatite
5.18G of calcium nitrate and 0.297g of yttrium chloride hexahydrate are weighed and dissolved in 100mL of distilled water, and a solution of calcium nitrate containing yttrium with the molar ratio of calcium to yttrium being 1.62:0.05 is prepared, and then 2.24g of ammonium dihydrogen phosphate is weighed and dissolved in 100mL of distilled water. Dropping the ammonium dihydrogen phosphate solution into the yttrium-containing calcium nitrate solution, maintaining the pH value of the reaction system at 9-10 by using 25% ammonia water by mass fraction, magnetically stirring at 300r/min for 12h, and aging for 24h under the conditions of 0.1MPa and 25 ℃. And (3) carrying out suction filtration, and freeze-drying the solid at the temperature of-80 ℃ for 72 hours to obtain the yttrium-doped nano-hydroxyapatite.
(2) Preparation of composite materials
Mixing yttrium-doped hydroxyapatite with zirconium dioxide powder according to a mass ratio of 1:1, and tabletting under the condition of room temperature under the pressure of 15 MPa. And sintering the obtained white biscuit at 1200 ℃ for 3 hours to obtain the composite material.
(3) Preparation of silk fibroin solution
Adding the crushed silk into 0.2mol/L NaHCO 3 solution, heating and boiling for 0.5h to remove colloid in the silk, taking out, washing twice with distilled water until the silk is neutral, drying in an oven at 80 ℃ for 2h, and taking out for later use. Respectively weighing 4.8g of NaOH and 7.2gCO g of distilled water (NH 2)2 is mixed with 100mL of distilled water to prepare NaOH and CO (NH 2)2) solution with the molar concentration of 1.2:8, putting degummed silk into the solution, heating to 60 ℃, preserving heat for 3h, and dialyzing the clear solution through a filter membrane to obtain a silk fibroin solution.
(4) Surface treatment of coated silk fibroin solutions
Cleaning the composite material obtained in the step (2) with deionized water and absolute ethyl alcohol in sequence, performing ultrasonic treatment for ten minutes, immersing a matrix into the silk fibroin solution for 2 hours, immersing into a calcium nitrate solution with the concentration of 32.5%, adding ammonia water to adjust the pH value, and maintaining the pH value at 9-10 to obtain the composite material coated with the calcium ion film;
(5) In situ mineralization
And (3) putting the composite material obtained in the step (4) into an ammonium dihydrogen phosphate solution with the concentration of 19.5% to mineralize for 24 hours, then drying in an oven at 80 ℃ for 2 hours, and washing and drying to obtain the yttrium-doped hydroxyapatite/zirconium dioxide composite material with the surface wrapped by the hydroxyapatite film.
The scanning electron microscope photograph of the nano hydroxyapatite/zirconium dioxide composite material with the surface coated by the hydroxyapatite film prepared in the embodiment is shown in fig. 5, and it can be seen that the hydroxyapatite is grown on the surface of the composite material in situ.
EXAMPLE 5 preparation of tetragonal zirconium dioxide/hydroxyapatite composite
(1) Preparation of rare earth doped nano hydroxyapatite
5.18G of calcium nitrate and 0.297g of yttrium chloride hexahydrate are weighed and dissolved in 100mL of distilled water, and a solution of calcium nitrate containing yttrium with the molar ratio of calcium to yttrium being 1.62:0.05 is prepared, and then 2.24g of ammonium dihydrogen phosphate is weighed and dissolved in 100mL of distilled water. Dropping the ammonium dihydrogen phosphate solution into the yttrium-containing calcium nitrate solution, maintaining the pH value of the reaction system at 9-10 by using 25% ammonia water by mass fraction, magnetically stirring at 300r/min for 12h, and aging for 24h under the conditions of 0.1MPa and 25 ℃. And (3) carrying out suction filtration, and freeze-drying the solid at the temperature of-80 ℃ for 72 hours to obtain the yttrium-doped nano-hydroxyapatite.
(2) Preparation of composite materials
Mixing yttrium-doped hydroxyapatite with zirconium dioxide powder according to a mass ratio of 1:1, and tabletting under the condition of room temperature under the pressure of 15 MPa. And sintering the obtained white biscuit at 1200 ℃ for 3 hours to obtain the composite material.
(3) Preparation of dopamine hydrochloride solution
10ML of 50mM Tris HCl solution is measured in a 50mL volumetric flask, water is added to fix the volume, 0.1238g of dopamine hydrochloride is accurately weighed and dissolved in the prepared Tris HCl solution, and the dopamine hydrochloride solution with the concentration of 2mg/mL is obtained for standby.
(4) Surface treatment of dopamine hydrochloride solutions
And (3) soaking the composite material obtained in the step (2) in a dopamine hydrochloride solution at a temperature of 37 ℃ for 24 hours.
(5) In situ mineralization
And (3) putting the composite material obtained in the step (4) into an ammonium dihydrogen phosphate solution with the concentration of 19.5% to mineralize for 24 hours, then drying in an oven at 80 ℃ for 2 hours, and washing and drying to obtain the yttrium-doped hydroxyapatite/zirconium dioxide composite material with the surface wrapped by the hydroxyapatite film.
The scanning electron microscope photograph of the nano hydroxyapatite/zirconium dioxide composite material with the surface wrapped by the hydroxyapatite film prepared in the embodiment is shown in fig. 6, and it can be seen that the hydroxyapatite is grown on the surface of the composite material in situ, and the coverage rate is higher than that of the embodiment 4, which indicates that the surface of the composite material is more easily mineralized to generate the hydroxyapatite by modifying the dopamine hydrochloride solution.
The yield strengths of the nano-hydroxyapatite/zirconia composites with surfaces coated with the hydroxyapatite film prepared in example 2, example 3, example 4 and example 5 are shown in table 2, and it can be seen that the yield strength of example 3 is significantly higher than that of example 2, indicating that the yield strength of the composite with 6% yttrium content is higher than that of the composite with 3% yttrium content, i.e. the yield strength increases with the increase of yttrium content; the nano hydroxyapatite/zirconium dioxide composite material with the surface wrapped by the hydroxyapatite film prepared in the example 3 and the example 4 has higher yield strength than that of the nano hydroxyapatite/zirconium dioxide composite material prepared in the example 2, which shows that the surface modification can ensure that the surface of the material is firmly connected with the outer layer of hydroxyapatite.
TABLE 2
| Sample of | Yield strength/MPa |
| Example 2 | 0.423 |
| Example 3 | 0.463 |
| Example 4 | 0.445 |
| Example 5 | 0.438 |
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (10)
1. The preparation method of the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material is characterized by comprising the following steps of:
(1) Preparation of rare earth doped nano hydroxyapatite
Adding calcium salt and rare earth salt into a solution, mixing, adding phosphate ion solution for reaction, controlling the molar ratio of calcium to rare earth in a reaction system to be (1.57-1.62) (0.05-0.10), controlling the molar ratio of calcium to rare earth to phosphorus to be 1.67, carrying out heat preservation mineralization on the obtained reaction solution, carrying out suction filtration, washing and freeze drying to obtain the rare earth doped nano hydroxyapatite;
the temperature of the heat preservation and mineralization is 20-25 ℃, the time is 24-36h, and the pressure is 0.1MPa;
(2) Preparation of tetragonal crystal form zirconium dioxide/hydroxyapatite composite material:
Mixing zirconium dioxide and the rare earth doped nano hydroxyapatite, and sintering to obtain the tetragonal crystal zirconium dioxide/hydroxyapatite composite material.
2. The process according to claim 1, wherein the reaction in step (1) is carried out at a temperature of 37 ℃ and at a pH of 9 to 10; the sintering temperature in the step (2) is 1100-1200 ℃ and the sintering time is 3-4h.
3. The method of claim 1, further comprising the step of performing an in situ mineralization treatment after step (2) of the method: and immersing the tetragonal crystal zirconium dioxide/hydroxyapatite composite material in a calcium salt solution, mineralizing in a phosphate radical solution, and sintering to obtain the tetragonal crystal zirconium dioxide/hydroxyapatite composite material.
4. The method of claim 1, further comprising the step of carrying out in situ mineralization after surface treatment with a silk fibroin solution after step (2) of the method:
Coating a silk fibroin solution on the surface of the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material for surface treatment, soaking the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material subjected to surface treatment in a calcium salt solution, mineralizing in a phosphate radical solution, and sintering to obtain the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material.
5. The method of preparing a silk fibroin solution according to claim 4, comprising the steps of:
Adding the colloid-removed silk into a mixed solution of NaOH and CO (NH 2)2), and treating at 60 ℃ for 3 hours to obtain the silk fibroin solution.
6. The method according to claim 1, further comprising the step of carrying out in-situ mineralization after the surface treatment with the dopamine hydrochloride solution after the step (2) of the method:
Soaking the surface of the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material in a dopamine hydrochloride solution for surface treatment, soaking the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material subjected to surface treatment in a calcium salt solution, mineralizing in a phosphate radical solution, and sintering to obtain the tetragonal crystal form zirconium dioxide/hydroxyapatite composite material.
7. The method according to claim 6, wherein the concentration of the dopamine hydrochloride solution is 2mg/mL.
8. The method according to any one of claims 3 to 7, wherein the sintering treatment is carried out at a temperature of 400 to 500 ℃ for a time of 2 to 3 hours.
9. The tetragonal zirconium dioxide/hydroxyapatite composite material prepared by the preparation method according to any one of claims 1 to 8.
10. Use of the tetragonal zirconia/hydroxyapatite composite material according to claim 9 as a bone repair material or a dental hard tissue repair material.
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