CN107601902B - Rubidium-containing bioglass ceramic and preparation method thereof - Google Patents
Rubidium-containing bioglass ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rubidium-containing bioglass ceramic, which comprises a glass phase and hydroxyapatite crystals, wherein rubidiumThe atoms are present in the glass phase. The preparation method comprises the following steps: (1) SiO raw material2、B2O3、CaO、Ca(H2PO4)2、RbCl、Na2O, ZnO and MgO are melted and clarified after being mixed evenly; (2) casting the clarified melt obtained in the step (1), and performing stress relief annealing; (3) and (3) heating the material obtained in the step (2) to 630-880 ℃, preserving heat for 5-10 h, and finally cooling along with the furnace to obtain the rubidium-containing biological glass ceramic. The bioglass ceramic contains a trace element Rb required by a human body, has an effect of improving cell activity, is good in biocompatibility, and controllable in Rb content, and the molar fraction of the Rb can reach 20% at most.
Description
Technical Field
The invention belongs to the field of biological materials, relates to a formula and preparation of biological ceramics, and particularly relates to a method for preparing alkali metal rubidium-containing biological glass ceramics by using a melting method.
Background
The glass ceramic is also called as microcrystalline glass, consists of a glass phase and a crystalline phase, has the superior performances of high mechanical strength, adjustable thermal expansion performance, thermal shock resistance, chemical corrosion resistance, low dielectric loss and the like, and has wide application in the fields of machinery, photoelectricity, chemical industry, biomedicine and the like. The biological glass ceramic has the main advantages that calcium and phosphorus are introduced into the glass, hydroxyapatite crystals can be separated out through heat treatment, and the biological glass ceramic has biocompatibility and bioactivity. Hydroxyapatite (Hydroxyapatite, chemical formula of Ca)10(PO4)6(OH)2Abbreviated as HA), is a main inorganic component of biological hard tissues such as natural bones and teeth, is a tissue engineering material, HAs the characteristics of bioactivity, biocompatibility, no toxicity, no rejection, certain mechanical strength, direct combination with bones and the like. The methods commonly used for preparing glass ceramics are melting, sintering and sol-gel methods.
Rubidium (Rb) is a group IA main group element of the fourth period in the chemical periodic table, and belongs to alkali metals with lithium, sodium, potassium and cesium. Rubidium is widely present in nature and in virtually all organisms, and is present at crust abundance at position 17. Rubidium is mainly applied to special glass at present, including optical fiber communication systems and night vision equipment, in particular to Rb2CO3Can reduce the conductive capability and improve the stability of the glassAnd durability. While the applications of Rb in the medical field are mainly divided into drugs and tracers, RbCl and some other rubidium salts can be used as density gradient media in ultracentrifugation for the separation of viruses, DNA or RNA; some rubidium salts can be used for preparing tranquilizers or hypnotics, and rubidium has a functional effect similar to potassium in organisms, has been used for 20 years for treating depression of human for long, and has low toxicity and high drug resistance; RbI is also sometimes used to replace KI in the treatment of goiter; because of the strict regulation of arsenic-containing drugs, some rubidium salts have been used to prepare anti-shock drugs; isotope of 85Rb82The Positron Emission from Rb β + decay process can be applied to Positron Emission Computed tomogry.
So far, the biomedical research on Rb is biased to the research on the nervous system, the application of Rb to the biological ceramic material is rarely researched, and the deep development and utilization of Rb resources are forced along with the discovery of a large rubidium ore in Tiantang mountain in Guangdong province in China.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a rubidium-containing bioglass ceramic and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a rubidium-containing bioglass ceramic comprising a glass phase and hydroxyapatite crystals, wherein rubidium atoms are present in the glass phase.
In the bioglass ceramic, preferably, the rubidium atoms exist in a glass phase and do not participate in the formation of hydroxyapatite crystals.
Preferably, the hydroxyapatite crystal is in a shape of a disk and/or a short rod, and is uniformly distributed in the glass phase.
As a general inventive concept, the present invention also provides a method for preparing the above rubidium-containing bioglass ceramic, comprising the steps of:
(1) SiO raw material2、B2O3、CaO、Ca(H2PO4)2、RbCl、Na2O, ZnO and MgO are melted and clarified after being mixed evenly;
(2) casting the clarified melt obtained in the step (1), and performing stress relief annealing;
(3) and (3) heating the material obtained in the step (2) to 630-880 ℃, preserving heat for 5-10 h, and finally cooling along with the furnace to obtain the rubidium-containing biological glass ceramic.
In the above preparation method, preferably, the raw materials respectively comprise the following components by mass:
in the above production method, the molar ratio of the Ca element to the P element in the raw material is preferably (0.5 to 2.0): 1; the RbCl in the raw materials accounts for 2 to 20 percent of the total mole percentage of the raw materials.
In the preparation method, preferably, in the step (1), the mixing process of the raw materials is performed on a mixer, and the mixing time is 16-28 hours; and transferring the mixed material to a muffle furnace, heating to 1150-1450 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 2-4 h to obtain a clarified melt.
Preferably, in the step (2), the clarified melt obtained in the step (1) is poured into a preheated graphite mold, then is immediately placed into a preheated muffle furnace, is subjected to heat preservation at 530-; the preheating of the graphite mold and the preheating of the muffle furnace are completed by placing the graphite mold into the muffle furnace, heating to 530-550 ℃, and preserving heat for 1-2 h.
In the preparation method, preferably, in the step (3), the heating rate during heating is 5 to 25 ℃/min.
The invention introduces Rb atoms into the bioglass ceramic, and finds that after the Rb atoms are introduced, the cell activity of the bioglass ceramic is improved and the microhardness of the material is reduced.
Compared with the prior art, the invention has the advantages that:
(1) the invention applies the Rb in the bioglass ceramic for the first time, so that the bioglass ceramic contains the trace element Rb required by a human body, has the effect of improving the cell activity, has good biocompatibility, and has controllable Rb content, and the molar fraction of the Rb can reach 20 percent at most.
(2) The bioglass ceramic formula system of the invention contains a plurality of substances with low melting points, including B2O3、Na2The O, the MgO and the ZnO can play a eutectic effect when the raw materials are melted, so that the melting point is reduced, the raw materials can be melted at 1300 ℃, and the uniformity of glass components can be ensured without secondary melting; the preparation method combines nucleation and growth processes into one, shortens time and reduces cost.
(3) The preparation method of the invention adds stress relief annealing in the traditional melting method, can effectively eliminate the internal stress generated when the glass ceramic is cooled from high temperature to room temperature, avoids the generation of cracks and improves the performance of the product.
(4) The hydroxyapatite glass ceramic has higher mechanical property, because the crystal of the hydroxyapatite is very small (in a shape of a round sheet or/and a short rod, the diameter and the length are both less than 1 mu m), the hydroxyapatite glass ceramic can play a role in fine grain strengthening, thereby improving the mechanical property of the glass ceramic.
Drawings
FIG. 1 is an X-ray diffraction analysis spectrum of bioglass ceramics of comparative example, examples 1-3 of the present invention after nucleation and growth.
FIG. 2 is a scanning electron micrograph of the bioglass ceramic of example 3 of the present invention after nucleation and growth.
FIG. 3 is an XPS (X-ray photoelectron spectroscopy) chart of bioglass ceramics of comparative example, examples 1 to 3, according to the present invention.
FIG. 4 is a graph showing cell culture activity of bioglass ceramics according to comparative examples and examples 1 to 3 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Comparative example:
the comparative example method for preparing a bioglass ceramic containing nano HA crystals includes the steps of:
(1) according to the mass fraction of each raw material component, the raw material components are respectively SiO2：17.6％、B2O3：16.9％、CaO：21.2％、Ca(H2PO4)2：29.6％、Na2O: 4.9%, ZnO: 4.9%, MgO: 4.9 percent of the raw materials are put into a mixer to be mixed for 18 hours;
(2) pouring the mixture mixed in the step (1) into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to 1320 ℃ at the speed of 15 ℃/min, and preserving heat for 2.5 hours to obtain a clarified melt;
(3) putting the graphite mold into a muffle furnace, heating to 530 ℃, preserving heat for 1h, and preheating;
(4) quickly pouring the clarified melt in the step (2) into the graphite mold preheated in the step (3), immediately putting the graphite mold into a preheated muffle furnace, preserving heat at 550 ℃ for 2 hours, removing stress, annealing, and cooling along with the furnace;
(5) taking out the sample in the step (4), putting the sample into a boat, and using Al2O3Covering the powder with a pressed compact, filling the pressed compact in a boat, heating to 740 ℃ at a speed of 15 ℃/min, preserving heat for 6h, and cooling along with the furnace to obtain the Rb-free bioglass ceramic.
Example 1:
the rubidium-containing bioglass ceramic comprises a glass phase and hydroxyapatite crystals, wherein rubidium atoms exist in the glass phase and do not participate in the formation of the hydroxyapatite crystals; the hydroxyapatite crystals are in the shapes of round sheets and short rods and are uniformly distributed in the glass phase.
The preparation method of the rubidium-containing bioglass ceramic comprises the following steps:
(1) according to the mass fraction of each raw material component, the raw material components are respectively SiO2：16.7％、B2O3：16.0％、CaO：20.0％、Ca(H2PO4)2：28.3％、RbCl：4.9％、Na2O: 4.7%, ZnO: 4.7%, MgO: 4.7 percent, putting the raw materials into a mixer, and mixing for 24 hours; wherein RbCl accounts for 3 percent of the total mole percentage of the raw materials;
(2) pouring the raw materials mixed in the step (1) into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to 1300 ℃ at a speed of 10 ℃/min, and preserving heat for 2.5 hours to obtain a clear melt;
(3) putting the graphite mould into a muffle furnace, heating to 540 ℃, preserving heat for 1h, and preheating;
(4) pouring the clarified melt in the step (2) into the preheated graphite mould in the step (3) quickly for casting, then immediately putting into a preheated muffle furnace, preserving heat at 550 ℃ for 1.5h for stress relief annealing, and then cooling along with the furnace;
(5) taking out the sample in the step (4), putting the sample into a boat, and using Al2O3Covering the powder with pressed blank and filling the boat with the powder, heating to 750 ℃ at the heating rate of 10 ℃/min, preserving heat for 6h, nucleating, growing up, and furnace cooling to obtain the bioglass ceramic with the rubidium molar content of 3%.
Example 2:
the rubidium-containing bioglass ceramic comprises a glass phase and hydroxyapatite crystals, wherein rubidium atoms exist in the glass phase and do not participate in the formation of the hydroxyapatite crystals; the hydroxyapatite crystals are in the shape of a disk and a short rod, and are uniformly distributed in the glass phase.
The preparation method of the rubidium-containing bioglass ceramic comprises the following steps:
(1) according to the mass fraction of each raw material component respectivelySiO2：15.8％、B2O3：15.2％、CaO：19.0％、Ca(H2PO4)2：27.0％、RbCl：9.8％、Na2O: 4.4%, ZnO: 4.4%, MgO: 4.4 percent, putting the raw materials into a mixer, and mixing for 24 hours; wherein RbCl accounts for 6 percent of the total mole percentage of the raw materials;
(2) pouring the raw materials mixed in the step (1) into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to 1300 ℃ at a speed of 10 ℃/min, and preserving heat for 2 hours to obtain a clear melt;
(3) putting the graphite mould into a muffle furnace, heating to 540 ℃, preserving heat for 1h, and preheating;
(4) quickly pouring the clarified melt in the step (2) into the graphite mold preheated in the step (3), immediately putting the graphite mold into a preheated muffle furnace, preserving heat at 550 ℃ for 1.5h for stress relief annealing, and cooling along with the furnace;
(5) taking out the sample in the step (4), putting the sample into a boat, and using Al2O3Covering the powder with a pressed compact and filling the pressed compact in a boat, heating to 750 ℃ at the heating rate of 10 ℃/min, preserving the heat for 7h, and cooling along with the furnace to obtain the HA glass ceramic with the Rb molar content of 6%.
Example 3:
the rubidium-containing bioglass ceramic comprises a glass phase and hydroxyapatite crystals, wherein rubidium atoms exist in the glass phase and do not participate in the formation of the hydroxyapatite crystals; the hydroxyapatite crystals are in the shapes of a disk and a short rod and are uniformly distributed in the glass phase, as shown in figure 2, the hydroxyapatite crystals in the shapes of a disk and a short rod can be seen, and the diameters and the lengths of the hydroxyapatite crystals are smaller than 1 mu m.
The preparation method of the rubidium-containing bioglass ceramic comprises the following steps:
(1) according to the mass fraction of each raw material component, the raw material components are respectively SiO2：14.7％、B2O3：14.1％、CaO：17.9％、Ca(H2PO4)2：25.1％、RbCl：15.9％、Na2O: 4.1%, ZnO: 4.1%, MgO: 4.1 percent of the total weight, putting the raw materials into a mixer, mixing the raw materials for 24 hours(ii) a Wherein RbCl accounts for 10 percent of the total mole percentage of the raw materials;
(2) pouring the raw materials mixed in the step (1) into a corundum crucible, putting the corundum crucible into a muffle furnace, heating to 1300 ℃ at a speed of 10 ℃/min, and preserving heat for 2 hours to obtain a clear melt;
(3) placing the graphite mold into a muffle furnace, heating to 550 ℃, preserving heat for 1h, and preheating;
(4) quickly pouring the clarified melt in the step (2) into the graphite mold preheated in the step (3), then immediately putting into a muffle furnace, preserving heat at 550 ℃ for 1h for stress relief annealing, and then cooling along with the furnace;
(5) taking out the sample in the step (4), putting the sample into a boat, and using Al2O3Covering the powder with a pressed compact and filling the pressed compact in a boat, heating to 760 ℃ at a heating rate of 10 ℃/min, preserving heat for 7h, and cooling with the furnace to obtain the bioglass ceramic with the rubidium molar content of 10%.
The X-ray patterns of the bioglass ceramics prepared in comparative example, examples 1-3 are shown in fig. 1, wherein a small amount of white calciumphophate is formed without rubidium addition and only hydroxyapatite crystals are formed after rubidium addition; the XPS of bioglass ceramics in the comparative example, examples 1-3, is shown in FIG. 3, the comparative example has no Rb element added, so there is no Rb peak, and there are Rb peaks in all of the other three examples; comparative example, example 1-3 bioglass ceramic cells (bone marrow mesenchymal stem cells, BMSCs) culture results As shown in FIG. 4, it was found that after Rb was added, the cell activity was not greatly affected within 24h, but after 72h, it was found that the cell activity of the bioglass ceramic with Rb added was significantly higher than that of the bioglass ceramic without Rb added, and as the content of Rb was increased, the cell activity also showed an increasing trend, indicating that the bioglass ceramic containing Rb has less cytotoxicity and better biocompatibility.
Physical properties of the bioglass ceramics of comparative example, examples 1 to 3 are shown in table 1, and it was found that the microhardness showed a decreasing tendency after Rb was added.
TABLE 1 physical Properties of bioglass ceramics of comparative example and examples 1 to 3
Claims (8)
1. A rubidium-containing bioglass ceramic comprising a glass phase and hydroxyapatite crystals, wherein rubidium atoms are present in the glass phase; and does not participate in the formation of hydroxyapatite crystals; the rubidium-containing bioglass ceramic comprises 10-30% of SiO by mass25-30% of B2O312 to 32% CaO, 14 to 51% Ca (H)2PO4)2And 1-27% RbCl.
2. The bioglass ceramic according to claim 1, characterized in that the hydroxyapatite crystals have a morphology of discs and/or short rods and are homogeneously distributed in the glass phase.
3. A method of making the rubidium-containing bioglass ceramic of claim 1, comprising the steps of:
(1) SiO raw material2、B2O3、CaO、Ca(H2PO4)2、RbCl、Na2O, ZnO and MgO are melted and clarified after being mixed evenly;
(2) casting the clarified melt obtained in the step (1), and performing stress relief annealing;
(3) and (3) heating the material obtained in the step (2) to 630-880 ℃, preserving heat for 5-10 h, and finally cooling along with the furnace to obtain the rubidium-containing biological glass ceramic.
4. The production method according to claim 3, wherein, in the raw materials, by mass:
Na2O 0.5~13.5%；
ZnO 0.5~15.5%；
MgO 0.5~11.5%。
5. the method according to claim 4, wherein the molar ratio of the Ca element to the P element in the raw material is (0.5 to 2.0): 1; the RbCl in the raw materials accounts for 2-20% of the total mole percentage of the raw materials.
6. The preparation method according to claim 3, wherein in the step (1), the raw materials are mixed on a mixer for 16-28 h; and transferring the mixed material to a muffle furnace, heating to 1150-1450 ℃ at a heating rate of 5-30 ℃/min, and preserving heat for 2-4 h to obtain a clarified melt.
7. The preparation method as claimed in claim 3, wherein in the step (2), the clarified melt obtained in the step (1) is poured into a preheated graphite mold, then immediately placed into a preheated muffle furnace, and subjected to heat preservation at 530 ℃ and 550 ℃ for 1-2h for stress relief annealing, and finally cooled along with the furnace; the preheating of the graphite mold and the preheating of the muffle furnace are completed by placing the graphite mold into the muffle furnace, heating to 530-550 ℃, and preserving heat for 1-2 h.
8. The method according to claim 3, wherein in the step (3), the heating rate is 5 to 25 ℃/min.
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| CN101693597A (en) * | 2009-11-02 | 2010-04-14 | 北京科技大学 | Novel transparent glass ceramics and preparation process thereof |
| CN103449725A (en) * | 2013-08-23 | 2013-12-18 | 四川大学 | Bioactive glass ceramic material and preparation method and application thereof in oral care products |
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| CN101693597A (en) * | 2009-11-02 | 2010-04-14 | 北京科技大学 | Novel transparent glass ceramics and preparation process thereof |
| CN103449725A (en) * | 2013-08-23 | 2013-12-18 | 四川大学 | Bioactive glass ceramic material and preparation method and application thereof in oral care products |
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