CN114409390A - Strontium-doped calcium borosilicate ceramic and preparation method and application thereof - Google Patents
Strontium-doped calcium borosilicate ceramic and preparation method and application thereof Download PDFInfo
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- CN114409390A CN114409390A CN202210108965.7A CN202210108965A CN114409390A CN 114409390 A CN114409390 A CN 114409390A CN 202210108965 A CN202210108965 A CN 202210108965A CN 114409390 A CN114409390 A CN 114409390A
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- Prior art keywords
- strontium
- calcium borosilicate
- doped calcium
- doped
- calcium
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 133
- 239000000919 ceramic Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 24
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- 229910052712 strontium Inorganic materials 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
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- 238000003756 stirring Methods 0.000 claims description 8
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- 235000011010 calcium phosphates Nutrition 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- 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 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 4
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
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- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
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- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 claims description 2
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- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 claims description 2
- 238000007569 slipcasting Methods 0.000 claims description 2
- 229910001631 strontium chloride Inorganic materials 0.000 claims description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- LNSYCBFBTCINRL-UHFFFAOYSA-N tristrontium;diborate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]B([O-])[O-].[O-]B([O-])[O-] LNSYCBFBTCINRL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001513 hot isostatic pressing Methods 0.000 claims 1
- 238000009768 microwave sintering Methods 0.000 claims 1
- 210000001185 bone marrow Anatomy 0.000 abstract description 14
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- 238000002386 leaching Methods 0.000 abstract description 13
- 230000009818 osteogenic differentiation Effects 0.000 abstract description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 4
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- 229910001427 strontium ion Inorganic materials 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 10
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 10
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- 102000002260 Alkaline Phosphatase Human genes 0.000 description 7
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- XXUPLYBCNPLTIW-UHFFFAOYSA-N octadec-7-ynoic acid Chemical compound CCCCCCCCCCC#CCCCCCC(O)=O XXUPLYBCNPLTIW-UHFFFAOYSA-N 0.000 description 2
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- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a strontium-doped calcium borosilicate ceramic and a preparation method and application thereof; the invention adopts a sol-gel method to synthesize pure-phase strontium-doped calcium borosilicate ceramic powder, and the chemical composition general formula of the powder is Ca11‑xSrxB2Si4O22Wherein 0 is<x is less than or equal to 0.20. Granulating, molding and sintering the prepared strontium-doped calcium borosilicate powder to obtain a ceramic block, and after the strontium-doped calcium borosilicate ceramic block is placed in simulated body fluid and soaked for 1 day, depositing a hydroxyapatite layer on the surface of the material; strontium-doped calcium borosilicate powder leaching liquorThe cell line is co-cultured with mouse bone marrow mesenchymal stem cells to show that the cell line has the capacity of promoting the osteogenic differentiation of the stem cells. The strontium-doped calcium borosilicate biomaterial prepared by the invention has good bioactivity and osteogenic differentiation performance, and can be used as a medical material for bone repair.
Description
Technical Field
The invention belongs to the field of biomedical materials, and particularly relates to strontium-doped calcium borosilicate ceramic as well as a preparation method and application thereof.
Background
The bone repair material mainly comprises allogeneic bone, autologous bone and synthetic bone repair material. Autologous bone grafting is the standard way of treating bone defects, without the risk of immune reactions; autologous bone grafting is the gold standard for bone defect repair, but the treatment mode of autologous bone grafting can cause the condition that patients suffer from secondary operation pain, and the available transplants are limited; allogenic bone transplantation can solve the problem of transplant supply, but still has the problems of causing immunological rejection reaction, cross infection and the like; the artificial bone repair material has the advantages of no immunological rejection, good biological activity and the like, and is widely concerned by researchers.
The wollastonite ceramic has excellent osteoconductivity and osteoinductivity, but has high material degradability and poor mechanical property, so that the rate of new bone generation is not matched with the rate of material degradation, and inflammation reaction can be caused by excessive local degradation. At present, network modification bodies are mostly adopted for modifying calcium-silicon-based ceramics, namely, alkali metal or alkaline earth metal ions are adopted for replacing calcium positions. According to CaO-B2O3-SiO2The ternary phase diagram shows that Ca can be separated out by proper formula composition and heat treatment system11B2Si4O22A calcium borosilicate crystalline phase, and in the crystalline structure, Ca acts as a network modifier to disrupt the network structure, B and Si act as network forming ions; compared with wollastonite, a proper amount of B is adopted to replace part of Si, the bonding strength of B-O is higher than that of Si-O, boron-oxygen coordination tetrahedrons can form a stronger network structure, the degradation rate of the material is reduced, the formation rate of new bones is matched with the degradation rate of the material as far as possible, and the mechanical property of the material is improved. B is a trace element necessary for human body, has proper amount and good biological safety, and has important effects in reducing the risk of osteoporosis and arthritis and inducing angiogenesis. Meanwhile, the bone immunology research finds that B can promote the osteogenic differentiation of stem cells and the macrophage differentiation from M1To M2The phenotypic polarization achieves the inflammation inhibiting effect. The calcium borosilicate bioceramic can release Si4+、Ca2+、B3+And the bioactive ions remarkably promote the proliferation and differentiation of bone tissue cells and the repair of bone tissues.
Sr is one of important trace elements in human body and accounts for0.05% of the calcium content in human bones. Studies show that Sr2+Has double functions on osteocytes, can stimulate the formation of new bones, inhibit the bone absorption of osteoclasts, reduce the fracture incidence and is widely applied to the treatment of osteoporosis. Sr2+With Ca2+Having similar ionic radii and charges, which is also Sr2+Doping replacement Ca2+Provides favorable conditions; sr in the process of bone formation2+Can replace Ca2+To promote bone remodeling. Sr2+Has effects in promoting bone metabolism and vascularization. Sr2+The calcium-sensing receptor (CaSR) on osteoblasts is activated, the expression of Osteoprotegerin (OPG) is enhanced, the expression of a nuclear factor kappa B receptor activator factor ligand (RANKL) is reduced, the CaSR and a downstream signal path of the osteoblasts can be activated, the proliferation and differentiation of the osteoblasts are promoted, and the apoptosis of osteoclasts is induced to reduce bone resorption. The preparation method of the Sr-doped calcium borosilicate is simple and easy to implement, has low energy consumption, has a single-phase preparation crystal phase, does not generate a heterogeneous phase, can simultaneously degrade and generate four ions of Ca, B, Si and Sr, improves the osteogenic performance of the material, and has good application value as a bone repair material.
Patent CN201310748645.9 discloses a calcium borosilicate biological material, a preparation method and a preparation method of application thereof, and calcium borosilicate (Ca) is synthesized by adopting a solid phase method or a wet chemical method11B2Si4O22) The powder synthesized by a solid phase method often has coarse grains, so that the calcination period is often longer and the calcination temperature is high in order to ensure the purity of the synthesized crystalline phase, and the prepared powder also needs mechanical ball milling due to serious agglomeration, so that the whole preparation procedure and cost are increased; the reported wet chemical method requires two times of sintering to prepare the calcium borosilicate powder.
Disclosure of Invention
In order to overcome the defects of poor osteoinductivity and low mechanical strength of the conventional biological ceramics in the prior art, the invention aims to provide the preparation method of the strontium-doped calcium borosilicate ceramic material.
The pure-phase calcium borosilicate powder is prepared by a sol-gel method, compared with a solid phase method and a wet chemical method, the preparation process is simple, the calcium borosilicate powder can be prepared by one-time heat treatment, the energy is saved, strontium is doped into crystal lattices of the calcium borosilicate, strontium ions are introduced, the calcium borosilicate degrades in body fluid to release four ions of Ca, B, Si and Sr, and the four ions have certain osteogenesis effect when existing independently, the material realizes the simultaneous release of the four ions, achieves a synergistic effect and simultaneously influences the generation of new bones, and compared with a single active ion, the osteogenesis performance of the calcium borosilicate ceramic can be obviously improved. The powder prepared by the sol-gel method has higher specific surface area and bioactivity, promotes the wider clinical application of the calcium borosilicate ceramic and has important social and economic values.
The purpose of the invention is realized by the following technical scheme:
a strontium-doped calcium borosilicate ceramic with a chemical composition formula of Ca11-xSrxB2Si4O22Wherein 0 is<x≤0.20。
The preparation method of the strontium-doped calcium borosilicate ceramic comprises the following steps:
(1) adding a calcium source, a strontium source, a boron source and a silicon source into deionized water or ethanol, adding an acidic solution to adjust the pH of the mixed solution to 4.0-7.0, and performing hydrolytic polycondensation reaction to obtain strontium-doped calcium borosilicate sol;
(2) standing, aging and drying the strontium-doped calcium borosilicate sol obtained in the step (1) to obtain strontium-doped calcium borosilicate xerogel;
(3) carrying out heat treatment on the strontium-doped calcium borosilicate xerogel obtained in the step (2) to obtain strontium-doped calcium borosilicate ceramic powder;
(4) and (4) granulating, sieving and molding the strontium-doped calcium borosilicate ceramic powder obtained in the step (3), and sintering to obtain the strontium-doped calcium borosilicate ceramic material.
Preferably, the calcium source in step (1) is at least one of calcium hydroxide, calcium nitrate, calcium chloride, calcium phosphate, calcium hydrogen phosphate and calcium lactate; the strontium source is at least one of strontium chloride, strontium nitrate, strontium carbonate and strontium sulfate; the boron source is at least one of boric acid, boron oxide and strontium borate; the silicon source is at least one of tetraethoxysilane, silicon acetate, methyl silicate, metasilicic acid and orthosilicic acid; the acidic solution is at least one of acetic acid, oxalic acid, citric acid, hydrochloric acid and nitric acid.
Preferably, the preparation of the mixed solution in the step (1) is specifically as follows: respectively preparing a calcium source precursor solution, a strontium source precursor solution, a boron source precursor solution and a silicon source precursor solution, pouring the silicon source precursor solution into deionized water, adding an acidic liquid to adjust the pH, uniformly stirring, and then uniformly stirring the three solutions of the calcium source precursor solution, the strontium source precursor solution and the boron source precursor solution and pouring the three solutions into the silicon source precursor solution with the adjusted pH together.
Preferably, the mixed solution in the step (1) comprises the following components in parts by weight:
preferably, the time of the hydrolytic polycondensation reaction in the step (1) is 6 to 12 hours;
preferably, the standing and aging time of the step (2) is 12-24 h; the drying temperature is 60-150 ℃, and the drying time is 6-48 h;
preferably, the temperature of the heat treatment in the step (3) is 650-1200 ℃, the time of the heat treatment is 0.5-6h, and the rate of temperature rise is 2-15 ℃/min.
Preferably, the forming method in the step (4) is at least one of dry pressing, cold isostatic pressing, 3D printing, slip casting, gel casting and tape casting; the adhesive used for granulation is one or more of polyvinyl butyral, polyvinyl pyrrolidone and polyvinyl alcohol.
Preferably, the sintering temperature in the step (4) is 700-1200 ℃, the sintering time is 0.5-3h, and the heating rate is 5-20 ℃/min.
Further preferably, the cold isostatic pressing process conditions are as follows: the pressure of the semi-dry pressing is 10-40MPa, and the pressure maintaining time is 0.5-2 min; the cold isostatic pressing pressure is 100-250MPa, and the pressure maintaining time is 0.5-5 min.
The strontium-doped calcium borosilicate ceramic is applied to preparation of bone repair materials.
The strontium-doped calcium borosilicate ceramic powder is prepared by a sol-gel method, and the strontium-doped calcium borosilicate ceramic is prepared by corresponding granulation, forming and sintering processes.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the strontium-doped calcium borosilicate crystal prepared by the invention has excellent bioactivity and osteogenic differentiation capacity; the calcium borosilicate crystal can be synthesized by high-temperature treatment at 650-1200 ℃, which shows that the synthesized calcium borosilicate crystal has higher thermal stability, and provides possibility for adding calcium borosilicate as an active substance into other inorganic materials for modification; by doping strontium into the calcium borosilicate network structure, the particle size of the calcium borosilicate crystal is larger and larger along with the increase of the doping amount, which shows that the introduction of strontium reduces the lattice stability of calcium borosilicate, so that the material is more favorable for releasing active ions in the degradation process, and the release of the active ions influences the bone formation performance.
(2) The strontium-doped calcium borosilicate ceramic is prepared for the first time, strontium ions are introduced into a calcium borosilicate crystal structure, the calcium ion diameter is similar to that of the strontium ions, the strontium replaces the calcium ion position, and the material is degraded to release Ca2+、B3+、Si4+、Sr2+Four active ions, greatly improvedThe bone forming performance and the bioactivity of the calcium borosilicate are good.
(3) The strontium-doped calcium borosilicate ceramic prepared by the invention has excellent mechanical properties, and has better compressive strength compared with calcium-magnesium-silicon bioactive ceramics; the mineralization performance in vitro can be compared with that of bioactive glass, which cannot be achieved by other calcium-magnesium-silicon bioactive ceramics.
Drawings
FIG. 1 is an XRD spectrum of calcium borosilicate powder without strontium in example 1.
FIG. 2 is a graph showing the compressive strength of the strontium-free calcium borosilicate ceramic of example 1.
FIG. 3 is a surface microscopic structure of the strontium-undoped calcium borosilicate powder of example 1 and the strontium-doped calcium borosilicate powders of examples 2 to 4.
FIG. 4 is a surface microstructure diagram of an un-strontium-doped calcium borosilicate ceramic of example 1 and a strontium-doped calcium borosilicate ceramic of example 2.
FIG. 5 is a micrograph of the strontium-undoped calcium borosilicate ceramic of example 1 after 1.5XSBF mineralization for 1 day.
FIG. 6 is a micrograph of the strontium doped calcium borosilicate ceramic of example 2 after 1.5XSBF mineralization for 1 day.
FIG. 7 is a micrograph of the strontium doped calcium borosilicate ceramic of example 3 after 1.5XSBF mineralization for 1 day.
FIG. 8 is a graph showing the cell proliferation of the non-strontium-doped calcium borosilicate powder of example 1, the strontium-doped calcium borosilicate ceramic leaching solution of examples 2 to 4, and the complete medium co-cultured with the mouse bone marrow mesenchymal stem cells for 1 day, 3 days, and 7 days, respectively.
FIG. 9 is a graph showing the quantitative results of ALP in the co-culture of the leaching solutions of strontium-undoped calcium borosilicate ceramics according to example 1 and the leaching solutions of strontium-doped calcium borosilicate ceramics according to examples 2 to 4, respectively, in a complete medium with mouse bone marrow mesenchymal stem cells for 7 days.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Preparing non-strontium-doped calcium borosilicate sol: pouring an ethyl orthosilicate solution into deionized water, adding a citric acid solution to adjust the pH value to 4.0, uniformly stirring three solutions of a calcium nitrate solution and a boron oxide solution until the three solutions are dissolved, pouring the three solutions into the ethyl orthosilicate solution with the well-adjusted pH value, and performing hydrolytic polycondensation on the solution for 6 hours to form a strontium-free calcium borosilicate sol; wherein the mass ratio of the ethyl orthosilicate, the calcium nitrate, the boron oxide and the deionized water is 20:46:4: 30;
(2) standing and aging the sol for 24h, drying at 100 ℃ for 24h, heating to 1200 ℃ at the speed of 15 ℃/min, and carrying out high-temperature heat treatment for 0.5h to obtain strontium-free calcium borosilicate bioactive powder;
(3) mixing strontium-free calcium borosilicate bioactive powder with a polyvinyl butyral binder, granulating, sieving by a 40-80 mesh sieve, carrying out cold isostatic pressing on the sieved granulated powder under the process conditions of 120MPa and pressure maintaining for 2min to prepare a strontium-free calcium borosilicate ceramic green body, and heating at the speed of 5 ℃/min to carry out high-temperature sintering at 1200 ℃ for 3h to obtain the strontium-free calcium borosilicate ceramic.
Fig. 1 a is an XRD spectrum of the synthesized strontium-free calcium borosilicate powder of example 1, and the prepared strontium-free calcium borosilicate powder is pure phase and contains no other impurities.
FIG. 2 is a graph of the compressive strength of the strontium-free calcium borosilicate ceramic of example 1 (data from two tests) at about 290MPa, showing a significant advantage over wollastonite, akermanite, amesite and diopside (Materials Science and Engineering: C,2017,72: 259-267).
Fig. 3 is a microscopic structure diagram of the strontium-undoped calcium borosilicate powder in example 1 and the strontium-doped calcium borosilicate powder synthesized in examples 2 to 4, and it can be seen from the diagrams that the particle size of the synthesized powder is larger and larger with the increase of the strontium ion doping amount, probably because the strontium ion doping reduces the thermal stability of the calcium borosilicate crystal, and the grain boundary diffusion is accelerated by the generation of a part of liquid phase at a high temperature stage.
Fig. 4 shows the surface microstructures of the samples of calcium borosilicate ceramic samples not doped with strontium in example 1 and the surface microstructures of the samples of calcium borosilicate ceramic samples doped with strontium in example 2 in a manner of a "and a" b ", respectively.
The strontium-free calcium borosilicate ceramic prepared in this example has a certain excellent bioactivity, and fig. 5 shows that a small amount of hydroxyapatite is formed on the surface of the ceramic after the ceramic is soaked in 1X SBF for 5 days.
Example 2
(1) Preparing strontium-doped calcium borosilicate sol: pouring an ethyl orthosilicate solution into deionized water, adding a citric acid solution to adjust the pH value to 7, uniformly stirring three solutions of a calcium phosphate solution, a strontium nitrate solution and a boric acid solution until the three solutions are dissolved, pouring the three solutions into the ethyl orthosilicate solution with the well-adjusted pH value, and performing hydrolytic polycondensation on the solution for 12 hours to form a strontium-doped calcium borosilicate sol; wherein the mass ratio of the ethyl orthosilicate, the calcium nitrate, the boron oxide, the strontium nitrate and the deionized water is 20:45.9:4:0.1: 30;
(2) standing and aging the sol for 24h, drying at 100 ℃ for 24h, heating to 1200 ℃ at the speed of 2 ℃/min, and carrying out high-temperature heat treatment for 6h to obtain strontium-doped calcium borosilicate bioactive powder;
(3) mixing strontium-doped calcium borosilicate powder with a polyvinyl alcohol binder, granulating, sieving by a 40-80 mesh sieve, carrying out cold isostatic pressing on the sieved granulated powder under the process conditions of 200MPa and pressure maintaining for 0.5min to prepare a strontium-doped calcium borosilicate ceramic green body, and heating at the speed of 20 ℃/min to carry out high-temperature sintering at the temperature of 700 ℃ for 0.5h to obtain the strontium-doped calcium borosilicate ceramic.
The strontium-doped calcium borosilicate ceramic prepared in this example has excellent bioactivity, wherein b in fig. 1 is an XRD spectrum of the strontium-doped calcium borosilicate powder synthesized in example 2, and the prepared strontium-doped calcium borosilicate powder is a pure phase and does not contain other impurities. Figure 6 shows that after 5 days of soaking in 1.5X SBF, a layer of hydroxyapatite was formed on the ceramic surface.
Example 3
(1) Preparing strontium-doped calcium borosilicate sol: pouring a solution of ethyl orthosilicate into deionized water, adding an acetic acid solution to adjust the pH value to 4, uniformly stirring three solutions of a calcium phosphate solution, a strontium carbonate solution and a boric acid solution until the three solutions are dissolved, pouring the three solutions into the solution of ethyl orthosilicate with well-adjusted pH value, and performing hydrolytic polycondensation on the solution for 6 hours to form strontium-doped calcium borosilicate sol; wherein the mass ratio of the ethyl orthosilicate, the calcium nitrate, the boron oxide, the strontium nitrate and the deionized water is 20:43:4:3: 30;
(2) standing and aging the sol for 24h, drying at 150 ℃ for 24h, heating to 1100 ℃ at the speed of 4 ℃/min, and carrying out high-temperature heat treatment for 3h to obtain strontium-doped calcium borosilicate bioactive powder;
(3) mixing strontium-doped calcium borosilicate powder with a polyvinyl butyral binder, granulating, sieving by a 40-80 mesh sieve, carrying out cold isostatic pressing on the sieved granulated powder under the process conditions of 200MPa and pressure maintaining for 0.5min to prepare a strontium-doped calcium borosilicate ceramic green body, and heating at the speed of 5 ℃/min to carry out 1150 ℃ high-temperature sintering for 3h to obtain the strontium-doped calcium borosilicate ceramic.
The strontium-doped calcium borosilicate ceramic prepared in this example has excellent bioactivity, and fig. 7 shows that after being soaked in 1.5XSBF for 5 days, a layer of hydroxyapatite is formed on the surface of the ceramic.
Example 4
(1) Preparing strontium-doped calcium borosilicate sol: pouring an ethyl orthosilicate solution into deionized water, adding an acetic acid solution to adjust the pH value to 6, uniformly stirring three solutions of a calcium phosphate solution, a strontium carbonate solution and a boric acid solution until the three solutions are dissolved, pouring the three solutions into the ethyl orthosilicate solution with the well-adjusted pH value, and performing hydrolytic polycondensation on the solution for 7 hours to form a strontium-doped calcium borosilicate sol; wherein the mass ratio of the ethyl orthosilicate, the calcium nitrate, the boron oxide, the strontium nitrate and the deionized water is 20:41:4:5: 30;
(2) standing and aging the sol for 24h, drying at 150 ℃ for 24h, heating to 1150 ℃ at the speed of 10 ℃/min, and carrying out high-temperature heat treatment for 2h to obtain strontium-doped calcium borosilicate bioactive powder;
(3) mixing strontium-doped calcium borosilicate powder with polyvinyl butyral/polyvinyl alcohol binder, granulating, sieving with 40-80 mesh sieve, cold isostatic pressing the sieved granulated powder under the process conditions of 200MPa and pressure maintaining for 0.5min to prepare a strontium-doped calcium borosilicate ceramic green body, and heating at the speed of 8 ℃/min to perform high-temperature sintering at 700 ℃ for 2h to obtain the strontium-doped calcium borosilicate ceramic.
Cell experiments
Measuring proliferation of cells: under aseptic conditions, the calcium borosilicate ceramic leaching solution prepared in examples 1 to 4 was co-cultured with mouse bone marrow mesenchymal stem cells as an experimental group, and the complete medium was co-cultured with mouse bone marrow mesenchymal stem cells as a blank group (labeled as example 1 sample, example 2 sample, example 3 sample, example 4 sample, blank group, respectively). Adding mouse bone marrow mesenchymal stem cell suspension before generation 9 into a pore plate, wherein the number of cells in each pore is 10000, and replacing the cells with leaching liquor or complete culture medium every other day in the culture process. After the cells were cultured for 1 day, 3 days and 7 days, the toxicity of the leachate to mouse bone marrow mesenchymal stem cells was determined.
FIG. 8 is a graph showing the results of cell proliferation in co-culture of the calcium borosilicate ceramic leaching solution prepared in example 1 without strontium-doped calcium borosilicate ceramic and in examples 2 to 4 with mouse bone marrow mesenchymal stem cells as an experimental group and a complete medium with mouse bone marrow mesenchymal stem cells as a blank group (labeled as example 1 sample, example 2 sample, example 3 sample, example 4 sample, blank group, respectively) for 1 day and 3 days. As can be seen from FIG. 8, the proliferation number of cells in the blank group is significantly higher than that of the strontium-doped calcium borosilicate ceramic leaching solution, which indicates that the material has a certain cytotoxicity, but compared with the strontium ion doping experimental group, the appropriate strontium ion doping amount can effectively improve the proliferation capacity of cells.
Determination of alkaline phosphatase expression: the calcium borosilicate ceramic leaching solution prepared in examples 1 to 4 was co-cultured with mouse bone marrow mesenchymal stem cells under aseptic conditions as an experimental group. Adding mouse bone marrow mesenchymal stem cell suspension before generation 9 into a pore plate, wherein the number of cells in each pore is 20000, and replacing the culture process with leaching liquor containing osteogenesis differentiation inducing components or conventional osteogenesis inducing liquid every other day. When the cells were cultured for 7 days, the expression of the alkaline phosphatase (ALP) activity of the cells was measured.
When the co-culture was performed for 7 days, mouse bone marrow mesenchymal stem cells in each sample group were taken and detected using an ALP quantitative kit. FIG. 9 is a graph showing the quantitative results of ALP in the co-culture of the strontium-doped calcium borosilicate ceramic according to example 1, the strontium-doped calcium borosilicate ceramic leaching solution prepared according to examples 2 to 4, and mouse bone marrow mesenchymal stem cells for 7 days.
As can be seen from fig. 9, the mouse bone marrow mesenchymal stem cells co-cultured with the strontium-doped calcium borosilicate ceramic leaching solution have better osteogenic differentiation capacity than the non-doped calcium borosilicate, and the strontium-doped calcium borosilicate leaching solution has higher alkaline phosphatase expression, which indicates that the doping of strontium ions further improves the osteogenic differentiation capacity of the calcium borosilicate.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. The strontium-doped calcium borosilicate ceramic is characterized by having a chemical composition general formula of Ca11-xSrxB2Si4O22Wherein 0 is<x≤0.20。
2. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 1, comprising the following steps:
(1) adding a calcium source, a strontium source, a boron source and a silicon source into deionized water or ethanol, adding an acidic solution to adjust the pH of the mixed solution to 4.0-7.0 to obtain a mixed solution, and performing a hydrolytic polycondensation reaction to obtain strontium-doped calcium borosilicate sol;
(2) standing, aging and drying the strontium-doped calcium borosilicate sol obtained in the step (1) to obtain strontium-doped calcium borosilicate xerogel;
(3) carrying out heat treatment on the strontium-doped calcium borosilicate xerogel obtained in the step (2) to obtain strontium-doped calcium borosilicate ceramic powder;
(4) and (4) granulating, sieving and molding the strontium-doped calcium borosilicate ceramic powder obtained in the step (3), and sintering to obtain the strontium-doped calcium borosilicate ceramic material.
3. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 2, wherein the calcium source in step (1) is at least one of calcium hydroxide, calcium nitrate, calcium chloride, calcium phosphate, calcium hydrogen phosphate and calcium lactate; the strontium source is at least one of strontium chloride, strontium nitrate, strontium carbonate and strontium sulfate; the boron source is at least one of boric acid, boron oxide and strontium borate; the silicon source is at least one of tetraethoxysilane, silicon acetate, methyl silicate, metasilicic acid and orthosilicic acid; the acidic solution is at least one of acetic acid, oxalic acid, citric acid, hydrochloric acid and nitric acid.
4. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 2, wherein the preparation of the mixed solution in the step (1) is specifically as follows: respectively preparing a calcium source precursor solution, a strontium source precursor solution, a boron source precursor solution and a silicon source precursor solution, pouring the silicon source precursor solution into deionized water, adding an acidic liquid to adjust the pH, uniformly stirring, and then uniformly stirring the three solutions of the calcium source precursor solution, the strontium source precursor solution and the boron source precursor solution and pouring the three solutions into the silicon source precursor solution with the adjusted pH together.
5. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 2, wherein the mixed solution in the step (1) comprises the following components in parts by mass:
6. the method for preparing strontium-doped calcium borosilicate ceramic according to claim 2, wherein the time of the hydrolytic polycondensation reaction in the step (1) is 6-12 h; the standing and aging time of the step (2) is 12-24 h; the drying temperature is 60-150 ℃, and the drying time is 6-48 h; the temperature of the heat treatment in the step (3) is 650-1200 ℃, the time of the heat treatment is 0.5-6h, and the heating rate is 2-15 ℃/min.
7. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 2, wherein the forming in step (4) is at least one of dry pressing, cold isostatic pressing, 3D printing, slip casting, gel casting and tape casting; the adhesive used for granulation is one or more of polyvinyl butyral, polyvinyl pyrrolidone and polyvinyl alcohol.
8. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 2, wherein the sintering temperature in step (4) is 700-1200 ℃, the sintering time is 0.5-3h, the heating rate is 5-20 ℃/min, and the sintering process can be at least one of common high temperature sintering, microwave sintering and hot isostatic pressing sintering.
9. The method for preparing strontium-doped calcium borosilicate ceramic according to claim 8, wherein the cold isostatic pressing process conditions are as follows: the pressure of the semi-dry pressing is 10-40MPa, and the pressure maintaining time is 0.5-2 min; the cold isostatic pressing pressure is 100-250MPa, and the pressure maintaining time is 0.5-5 min.
10. Use of the strontium-doped calcium borosilicate ceramic of claim 1 in the preparation of a bone repair material.
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