CN109399943B

CN109399943B - Bioactive glass and preparation method thereof, microcrystalline glass and preparation method and application thereof

Info

Publication number: CN109399943B
Application number: CN201811369263.4A
Authority: CN
Inventors: 苏隽; 王德俊
Original assignee: Hangzhou Namei Zhikang Technology Co ltd
Current assignee: Hangzhou Namei Zhikang Technology Co ltd
Priority date: 2018-11-16
Filing date: 2018-11-16
Publication date: 2021-07-09
Anticipated expiration: 2038-11-16
Also published as: CN109399943A

Abstract

The invention provides bioactive glass and a preparation method thereof, microcrystalline glass and a preparation method and application thereof, and relates to the technical field of glass, wherein the bioactive glass comprises the following raw materials in percentage by mass: SiO 2₂ 40～60％、CaO 20～30％、P₂O₅ 5～12％、Na₂O 8～13％、ZnO 0.5～1.5％、SnO₂0.5-1.5 percent of SrO, 0.5-1.5 percent of SrO and 0.5-1.5 percent of F, and solves the technical problems that the prior bioactive glass easily loses bioactivity and influences the repair effect in the use process.

Description

Bioactive glass and preparation method thereof, microcrystalline glass and preparation method and application thereof

Technical Field

The invention relates to the technical field of glass, in particular to bioactive glass and a preparation method thereof, microcrystalline glass and a preparation method and application thereof.

Background

The bioactive glass is an important inorganic non-metal bone, tooth and skin wound repairComposite material, consisting essentially of SiO₂、CaO、Na₂O、P₂O₅The degradation product of the inorganic glass can promote the generation of growth factors, promote the multiplication of cells, and enhance the gene expression of osteoblasts and the growth of bone tissues; meanwhile, the bioactive glass body can perform ion exchange in a human body environment to form a bioactive hydroxyapatite layer, so that a bonding interface is provided for tissues. However, the existing bioactive glass easily loses bioactivity in the using process and influences the repairing effect.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The invention aims to provide bioactive glass to solve the technical problem that the prior bioactive glass easily loses bioactivity and influences the repair effect in the using process.

The invention provides bioactive glass which comprises the following raw materials in percentage by mass: SiO 2₂ 40～60％、CaO 20～30％、P₂O₅ 5～12％、Na₂O 8～13％、ZnO 0.5～1.5％、SnO₂0.5-1.5%, SrO 0.5-1.5% and F0.5-1.5%;

preferably, the bioactive glass is a bioactive glass powder;

more preferably, the particle size of the bioactive glass powder is 300-500 meshes.

Further, CaO and P₂O₅The mass ratio of (A) to (B) is 2.5 to 4, preferably 3 to 4.

Further, said Na₂The content of O is 10-12.8%, preferably 11.5-12.5%;

and/or, the SiO₂The content of (b) is 45 to 58%, preferably 50 to 55%.

The second purpose of the invention is to provide a preparation method of the bioactive glass, which comprises the following steps: mixing SiO₂、CaO、P₂O₅、Na₂O、ZnO、SnO₂SrO and F are mixed uniformly, melted at 1400-1600 ℃ for 4-7 h, quenched at 400 ℃ -Annealing at 600 ℃ for 1-2 h to obtain the bioactive glass.

Further, the melting temperature is 1500-1600 ℃, and preferably 1500-1550 ℃;

and/or the annealing temperature is 450-550 ℃, preferably 480-520 ℃.

The third purpose of the invention is to provide microcrystalline glass prepared by the bioactive glass provided by the invention;

preferably, the microcrystalline glass is microcrystalline glass powder;

more preferably, the microcrystalline glass powder has a particle size of 300 to 500 mesh.

Further, the microcrystalline glass comprises wollastonite main crystal grains and a hydroxyapatite crystal grain phase;

preferably, the particle size of the wollastonite crystal grain is 100-200 nm;

preferably, the particle size of the hydroxyapatite is 100-200 nm.

The fourth object of the present invention is to provide a method for producing the above-mentioned glass ceramics, comprising the steps of: carrying out heat treatment on the bioactive glass at the temperature of 600-900 ℃ for 3-7 h to obtain microcrystalline glass;

preferably, the bioactive glass is a bioactive glass powder,

Further, the heat treatment comprises a crystallization nucleation stage and a crystallization growth stage, wherein the temperature of the crystallization nucleation stage is 600-750 ℃, the time is 1-3 hours, the temperature of the crystallization growth stage is 700-900 ℃, and the time is 2-4 hours;

preferably, the temperature of the crystallization nucleation stage is 650-710 ℃ for 1-2.5 h, and the temperature of the crystallization growth stage is 760-850 ℃ for 2-3.5 h.

The fifth purpose of the invention is to provide the application of the bioactive glass in preparing the oral disease medicament.

The sixth purpose of the invention is to provide the application of the microcrystalline glass in preparing oral disease drugs.

The bioactive glass provided by the invention passes through SiO₂、CaO、P₂O₅、Na₂O、ZnO、SnO₂The SrO and the F are mutually cooperated, a large amount of hydroxyapatite can be generated on the surface of the artificial saliva after the artificial saliva acts for 72 hours, and elements of zinc, tin, strontium and fluorine are dissolved out, so that the loss of biological activity is effectively avoided, the growth of cell tissues and the differentiation of osteoblasts can be promoted, the growth of cancer cells can be inhibited, the formation of protein and nucleic acid is promoted, and the promotion of the health and the growth and development of human bodies are facilitated.

The microcrystalline glass provided by the invention can generate a large amount of hydroxyapatite by reacting the bioactive glass with the artificial saliva for 24 hours, and dissolves out zinc, tin, strontium and fluorine elements, thereby not only effectively avoiding loss of bioactivity, but also promoting cell tissue growth and osteoblast differentiation, simultaneously inhibiting cancer cell growth, promoting formation of protein and nucleic acid, and being more beneficial to promoting human health and growth and development.

Drawings

FIG. 1 is an XRD spectrum of a microcrystalline glass provided in examples 10 to 13;

FIG. 2 is an XRD spectrum of the microcrystalline glass powder provided in comparative examples 12-15;

FIG. 3 is an XRD spectrum of the microcrystalline glass powder provided in comparative examples 16 to 17 and examples 17 to 18;

FIG. 4 is an XRD spectrum of the microcrystalline glass powder provided in comparative examples 18-21;

FIG. 5 shows XRD spectra of microcrystalline glass powders and Ca in standard cards obtained in examples 17 to 18₁₀(PO₄)₆(OH)₂XRD spectrum of (1);

FIG. 6 is a DTA curve of the glass-ceramic powder provided in examples 10 to 13;

FIG. 7(a) is an appearance profile of a glass-ceramic provided in example 10;

FIG. 7(b) is an appearance profile diagram of a glass ceramic provided in example 11;

FIG. 7(c) is an appearance profile of a glass-ceramic provided in example 12;

FIG. 7(d) is a graph of the appearance and morphology of the glass-ceramic provided in example 13;

fig. 8(a) is an SEM topography of the glass-ceramic provided in example 10;

fig. 8(b) is an SEM topography of the glass-ceramic provided in example 11;

fig. 8(c) is an SEM topography of the glass-ceramic provided in example 12;

fig. 8(d) is an SEM topography of the glass-ceramic provided in example 13;

FIG. 9 is an XRD pattern of the bioactive glass powder provided in example 4 at 24h, 48h and 72h in contact with artificial saliva;

fig. 10 is an XRD spectrum of the microcrystalline glass powder provided in example 13 at 0h, 24h, 48h and 72h in contact with artificial saliva.

Detailed Description

The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that:

in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.

In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.

In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.

In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values.

The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.

In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.

Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.

According to one aspect of the invention, the invention provides bioactive glass, which comprises the following raw materials in percentage by mass: SiO 2₂ 40～60％、CaO 20～30％、P₂O₅ 5～12％、Na₂O 8～13％、ZnO 0.5～1.5％、SnO₂0.5 to 1.5%, SrO 0.5 to 1.5%, and F0.5 to 1.5%.

In the present invention, SiO₂Is an important component of bioactive glass, is a framework component of the bioactive glass and can influence the bioactivity of the glass. SiO 2₂When the content is too small or too large, not only is it difficult to form glass, but also the glass is rendered inactive for life. To ensure bioactivity and ease of glass formation, SiO₂The content of (B) is set to 40-60%.

In the bioactive glass raw material provided by the invention, SiO₂Such as 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60% by weight, as a typical but non-limiting example.

In the present invention, CaO and P₂O₅Is hydroxyapatite (Ca)₁₀(PO₄)₆(OH)₂) Forming components, theoretically, CaO and P₂O₅The higher the content of (A), the more advantageous the formation of hydroxyapatite, but CaO and P₂O₅Too high a content of (b) can significantly affect the viscosity of the glass melt and thus the properties of the bioactive glass. For ensuring the performance of bioactive glass, of CaOThe content is set to 20-30%, P₂O₅The content of (b) is set to 5 to 12%.

Typical but not limiting mass percentages of CaO in the bioactive glass feedstock provided by the present invention are, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%; p₂O₅Such as 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11% or 12% by weight.

In the present invention, Na₂O is a fluxing agent for preparing bioactive glass, the fluxing effect is more obvious along with the increase of the content of the fluxing agent, but when Na is used₂After the content of O is higher than 13%, Na₂O is easy to participate in the formation of crystal phase, so that the glass is crystallized to separate out the more easily crystallized Na-containing mineral crystal phase (such as Na)₂Ca₄(PO₄)₂SiO₄,NaAlSiO₄Etc.), thereby inhibiting hydroxyapatite (Ca)₁₀(PO₄)₆(OH)₂) And (4) crystal phase precipitation. Comprehensively considering that the glass is easy to melt and hydroxyapatite can be separated out after the glass is crystallized, and adding Na₂The content of O is set to 8 to 13%.

In the bioactive glass raw material provided by the invention, Na₂Typical but not limiting mass percentages of O are for example 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12% or 13%.

In medical application, a proper amount of the F element is beneficial to preventing the teeth from being damaged and forming hard outer layers of the teeth; the proper amount of Zn element is favorable for the growth and differentiation of tissue cells and is a component of various enzymes of a human body; a proper amount of Sr is beneficial to promoting tissue growth and osteoblast differentiation, reducing bone resorption and the like; the proper amount of Sn is favorable for inhibiting cancer cells, promoting the formation of protein and nucleic acid and being favorable for the growth and development of human bodies. F. Zn, Sr and Sn are all trace elements required by human body, and the content of the elements is not too much; while simultaneously being such as CaF₂，ZnO，SnO₂These substances can act as nucleating agents, and too high a content thereof affects the devitrification of the glass ceramics. Thus, of ZnOThe content is set to 0.5-1.5%, SnO₂The content of (A) is 0.5 to 1.5%, the content of SrO is 0.5 to 1.5%, and the content of F is 0.5 to 1.5%.

Typical but not limiting mass percentages of ZnO in the bioactive glass feedstock provided by the present invention are, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, or 1.5%; SnO₂Such as 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5% by mass; a typical but non-limiting percentage of SrO is, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%; typical but non-limiting percentages of F are for example 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%.

In a preferred embodiment of the invention, the bioactive glass is a bioactive glass powder. By setting the bioactive glass as the bioactive glass powder, it is convenient to apply it to the treatment of oral diseases, especially when the particle size of the bioactive glass powder is 300-500 mesh, the bioactive glass powder can effectively penetrate into dentinal tubules or precipitate on the surface of dentin, so that hydroxyapatite starts to form on the surface of dentin in the presence of oral liquid and is bonded to the dental tissue by chemical bonding.

In a preferred embodiment of the invention, the bioactive glass powder has a typical, but non-limiting, particle size such as 300 mesh, 320 mesh, 350 mesh, 380 mesh, 400 mesh, 420 mesh, 450 mesh, 480 mesh and 500 mesh.

In a preferred embodiment of the invention, CaO and P₂O₅The mass ratio of (A) to (B) is 2.5 to 4:1, preferably 3 to 4: 1. CaO and P₂O₅Can significantly affect the viscosity of the bioactive glass. When the ratio of the two is higher than 4, the hydroxyapatite is not suitable to be completely generated, and when the ratio of the two is lower than 2.5, the viscosity of the glass melt is very high, the melting difficulty is high, the preparation difficulty is high, and the bioactive glass is not easy to generate; when the ratio of the two is 2.5-3, the viscosity of the glass melt is reduced, and the glass melt can be melted at a higher temperature; particularly, when the ratio of the two is 3-4, the melt viscosity is moderate, and the melting is easier.

In a preferred embodiment of the invention, Na₂The content of O is 10-12.8%. By mixing Na₂The content of O is set to 10-12.8%, so that the melting of all raw materials can be guaranteed, and the precipitation of hydroxyapatite can be guaranteed; especially when Na is present₂Na when the content of O is 11.5-12.5%₂The fluxing effect of O is better, and the precipitation of hydroxyapatite can be accelerated.

In a preferred embodiment of the invention, SiO₂The content of (b) is 45 to 58%, preferably 50 to 55%. When the bioactive glass raw material is SiO₂When the content of (A) is 45-58%, the bioactive glass prepared by the method can be ensured to have good bioactivity, and the formation of a glass framework can be ensured, especially when SiO is used₂When the content of (a) is 50-55%, the prepared bioactive glass has better bioactivity.

The preparation of the bioactive glass mainly comprises the traditional sol-gel method and a high-temperature dissolution method, the hydroxyapatite microcrystalline glass with high bioactivity can be easily prepared by the sol-gel method, but the method has higher economic cost and time cost and is not suitable for large-scale production. The high-temperature fusion method for preparing the bioactive glass has low cost and short period, and is very suitable for large-scale production.

According to a second aspect of the present invention, there is provided a method for preparing the above bioactive glass by a high temperature fusion method, comprising the steps of:

mixing SiO₂、CaO、P₂O₅、Na₂O、ZnO、SnO₂And uniformly mixing the SrO and the F, melting for 4-7 h at 1400-1600 ℃, quenching, and annealing for 1-2 h at 400-600 ℃ to obtain the bioactive glass.

In the invention, the raw materials of the bioactive glass are melted at 1400-1600 ℃ for 4-7 h, so that the raw materials of the bioactive glass are melted, and the raw materials can fully interact and cooperate with each other to generate the bioactive glass. Through annealing at 400-600 ℃ for 1-2 h, the stability of the performance of the bioactive glass is ensured, and the influence on the performance of the bioactive glass caused by too fast annealing is avoided.

The bioactive glass provided by the invention is prepared by a high-temperature fusion method, has low cost and short period, and is very suitable for large-scale production.

Typical, but non-limiting, temperatures for melting in the present invention are, for example, 1400, 1420, 14050, 1480, 1500, 1520, 1550, 1580, or 1600 ℃; typical but not limiting times for melting are for example 4, 4.5, 5, 5.5, 6, 6.5 or 7 h.

In a preferred embodiment of the present invention, the melting temperature is 1500-1600 ℃, preferably 1500-1550 ℃. The melting temperature is set to be 1500-1600 ℃, so that the complete melting of all raw materials of the bioactive glass is facilitated, the melting efficiency is improved, and the preparation cost is reduced; particularly, when the melting temperature is 1500-1550 ℃, the energy consumption is lower and the preparation cost is lower.

In a preferred embodiment of the present invention, the annealing temperature is 450 to 550 ℃, preferably 480 to 520 ℃. The annealing temperature is controlled to be 450-550 ℃, so that the defects of cracks and the like in the bioactive glass caused by over-quick cooling are avoided, and the performance stability of the bioactive glass is ensured; particularly, when the annealing temperature is 480-520 ℃, the performance of the prepared bioactive glass is more stable and excellent.

In a preferred embodiment of the present invention, quenching includes, but is not limited to, water quenching and oil quenching.

According to a third aspect of the invention, the invention provides a microcrystalline glass prepared from the bioactive glass provided by the invention.

The raw materials of the microcrystalline glass provided by the invention are completely the same as those of bioactive glass, and are not described again.

In a preferred embodiment of the present invention, the microcrystalline glass is a microcrystalline glass powder, and the grain size of the microcrystalline glass powder is preferably 300 to 500 mesh. By setting the microcrystalline glass to the microcrystalline glass powder, it is possible to facilitate its application in the treatment of oral diseases, particularly when the microcrystalline glass powder has a particle size of 300 to 500 mesh, the microcrystalline glass powder can effectively penetrate into the dentinal tubules or precipitate on the dentinal surface, so that hydroxyapatite starts to form on the dentinal surface in the presence of oral liquid and is bonded to the dental tissue by chemical bonding.

In a preferred embodiment of the invention, the microcrystalline glass powder has typical, but not limiting, particle sizes such as 300 mesh, 320 mesh, 350 mesh, 380 mesh, 400 mesh, 420 mesh, 450 mesh, 480 mesh and 500 mesh.

In a preferred embodiment of the invention, the glass-ceramic comprises wollastonite (CaSiO)₃) Grains and hydroxyapatite (Ca)₁₀(PO₄)₆(OH)₂) The crystal grains enable wollastonite crystal grains and hydroxyapatite crystal grains to be quickly converted into hydroxyapatite when the microcrystalline glass acts with artificial saliva.

In a preferred embodiment of the present invention, the apatite crystal grains in the glass-ceramic are a primary crystal phase, and the hydroxyapatite crystal grains are a secondary crystal phase.

In a further preferred embodiment of the present invention, the wollastonite crystal particle has a particle size of 100 to 200 nm; the particle size of the hydroxyapatite crystal grains is 100-200 nm, so that the mass generation of hydroxyapatite on the surface of the glass ceramics is promoted.

In a preferred embodiment of the invention, the wollastonite grains have a typical, but not limiting, particle size such as 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, or 200 nm; typical but not limiting particle sizes of the hydroxyapatite grains are for example 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 nm.

According to a fourth aspect of the present invention, the present invention provides a method for preparing the above microcrystalline glass, including the steps of: grinding the bioactive glass into bioactive glass powder, and carrying out heat treatment on the bioactive glass at the temperature of 600-900 ℃ for 3-7 h to obtain the glass ceramics.

According to the invention, the bioactive glass powder is subjected to heat treatment to promote the growth of wollastonite crystal grains, so that wollastonite crystal grains and hydroxyapatite crystal grains are formed in the microcrystalline glass, and the surface of the microcrystalline glass is promoted to rapidly generate a large amount of hydroxyapatite.

Typical but non-limiting temperatures for heat treatment in the present invention are, for example, 600, 620, 650, 680, 700, 720, 750, 780, 800, 820, 850, 880 or 900 ℃; typical but not limiting times for the heat treatment are e.g. 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 4.8, 5, 5.2, 5.5, 5.8, 6, 6.2, 6.5, 6.8 or 7 h.

In a preferred embodiment of the invention, the bioactive glass is a bioactive glass powder. The bioactive glass powder is adopted for heat treatment, which is more beneficial to the formation of wollastonite crystal grains and hydroxyapatite crystal grains, thereby obtaining microcrystalline glass; especially, when the particle size of the bioactive glass powder is 300-500 meshes, the bioactive glass powder is easier to be converted into the glass ceramics.

In a preferred embodiment of the invention, the heat treatment comprises a crystallization nucleation stage and a crystallization growth stage, wherein the temperature of the crystallization nucleation stage is 600-750 ℃ and the time is 1-3 h, and the temperature of the crystallization growth stage is 700-900 ℃ and the time is 2-4 h. The bioactive glass is subjected to heat treatment at 600-750 ℃ for 1-3 hours, so that wollastonite crystal nuclei and hydroxyapatite crystal nuclei are generated in the bioactive glass, and particularly, the bioactive glass is subjected to heat treatment at 650-710 ℃ for 1-2.5 hours, so that more wollastonite crystal nuclei and more hydroxyapatite crystal nuclei are generated; and then, performing heat treatment at 700-900 ℃ for 2-4 h to enable wollastonite crystal nuclei and hydroxyapatite crystal nuclei to grow into wollastonite crystal grains and hydroxyapatite crystal grains respectively, so as to obtain the glass ceramics, and particularly performing heat treatment at 600-850 ℃ for 2-3.5 h to produce the wollastonite crystal grains and the hydroxyapatite crystal grains with better grain size distribution uniformity more easily, so that the performance of the glass ceramics is more stable.

In a preferred embodiment of the present invention, typical but not limiting temperatures of the crystallization nucleation stage are, for example, 600, 620, 650, 680, 700, 710, 720 or 750 ℃, and typical but not limiting times are, for example, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8 or 3 hours; typical but not limiting temperatures for the crystalline growth phase are 700, 720, 750, 760, 780, 800, 820, 850, 880 or 900 deg.C, and typical but not limiting times are 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8 or 4 hours.

According to a fifth aspect of the present invention there is provided the use of a bioactive glass in the manufacture of a medicament for the treatment of oral diseases.

According to a sixth aspect of the invention, the invention provides the use of glass ceramics in the manufacture of a medicament for the treatment of oral diseases.

In the present invention, oral diseases include, but are not limited to, tooth sensitivity, cleft teeth, and xerostomia.

In a preferred embodiment of the invention, the bioactive glass and/or the microcrystalline glass can be used as an additive of toothpaste, promotes remineralization of tooth surfaces and can effectively prevent dental caries.

The technical solution provided by the present invention is further described below with reference to examples and comparative examples.

Bioactive glass

Examples 1 to 9 and comparative examples 1 to 11 each provide a bioactive glass powder having a raw material composition shown in table 1.

Table 1 bioactive glass raw material composition data table

The raw materials of the bioactive glasses provided in examples 1 to 9 and comparative examples 1 to 11 were respectively put in a corundum crucible (Al)₂O₃) The preparation method comprises the steps of uniformly mixing, melting for 6 hours at 1500-1600 ℃, water quenching, annealing for 2 hours at 500 ℃, grinding and sieving with a 300-mesh sieve to obtain the bioactive glass powder. The melting conditions in the preparation processes of the bioactive glass powders provided in examples 1 to 9 and comparative examples 1 to 11 were recorded, and the bioactive glass powders provided in examples 1 to 9 and comparative examples 1 to 11 were respectively acted on artificial saliva, and after 24 hours of action, the dissolution conditions of trace elements were recorded, and after 72 hours of action, the precipitation conditions of crystal phases were recorded, and the results are shown in table 2.

TABLE 2 bioactive glass melting and precipitation after interaction with artificial saliva

As can be seen from the examples in table 2, the bioactive glass powders provided in examples 1 to 9 can dissolve all Zn, Sn, Sr, and F after 24 hours of action with artificial saliva, and can precipitate a large amount of hydroxyapatite after 72 hours of action with artificial saliva, thereby playing a role in repair. This shows that the bioactive glass powder provided in examples 1 to 9 not only has good bioactivity, but also can promote the growth of cell tissues and the differentiation of osteoblasts, and simultaneously can inhibit the growth of cancer cells, promote the formation of proteins and nucleic acids, and is more beneficial to the promotion of human health and growth and development.

As can be seen from the comparison of examples 1 to 7 with examples 8 to 9, when CaO and P are present₂O₅When the mass ratio of (A) to (B) is between 3 and 4, each raw material is easier to melt at 1500 ℃, and when CaO and P are contained₂O₅When the mass ratio of (A) to (B) is 2, the melting is very difficult to be carried out at 1500 ℃, and the melting can be finished only at the temperature of more than 1500 ℃, so that the preparation difficulty is increased, and the method is not suitable for large-scale production.

As can be seen from the comparison of examples 1 to 4 and examples 6 to 7 with example 5, CaO and P are present₂O₅When the mass ratio of (A) to (B) is 2.5-3, the melting of each raw material at 1500 ℃ is slightly difficult, and the melting can be completed only by raising the temperature to 1600 ℃.

As can be seen from comparative examples 1 to 10, when Na is used₂The content of O is higher than 13%, and the crystal phase separated out after the bioactive glass acts with artificial saliva 24 is Na₂Ca₄(PO₄)₂SiO₄And NaAlSiO₄And no hydroxyapatite was produced, indicating Na₂Too high of O content results in Na₂O participates in the formation of a crystal phase, so that the crystal phase can not react with artificial saliva to generate hydroxyapatite, and the bioactive glass provided by the comparative examples 1-10 has no bioactivity and can not play a therapeutic role.

In addition, it can be seen from comparative examples 1 to 5 that CaO and P₂O₅When the mass ratio of (A) to (B) is 2, the raw materials are difficult or difficult to melt at 1500 ℃, the preparation difficulty is high, the melting temperature is high, the cost is high, and the large-scale production is difficult to carry out.

As can be seen from the comparison between example 4 and comparative example 11, ZnO and SnO were added to the raw materials₂The SrO and the F can react with the artificial saliva for 24 hours to precipitate Zn, Sn, Sr and F elements, thereby better promoting the health and growth of human bodies.

It should be noted that some of the precipitated phases of the comparative examples include NaAlSiO₄Because the corundum crucible participates in the melting process in the process of melting the raw materials, Al element is introduced, and the precipitated phase contains NaAlSiO₄。

(II) microcrystalline glass

Examples 10-18 and comparative examples 12-21 each provide a microcrystalline glass powder made from the bioactive powders provided in examples 1-9 and comparative examples 1-10, respectively, each prepared according to the following steps: respectively carrying out heat treatment on the bioactive glass powder at 660 ℃ for 2h to generate crystal nuclei, then carrying out heat treatment at 850 ℃ for 3h to grow the crystal nuclei into crystal grains, cooling, grinding and sieving by using a 300-mesh sieve to obtain the microcrystalline glass powder.

Test example 1

The microcrystalline glass powders provided in examples 10 to 18 and comparative examples 12 to 21 were allowed to act on artificial saliva for 24 hours, and then the elution of trace elements and the precipitation of crystal phases were recorded, and the results are shown in table 3.

TABLE 3 precipitation of glass ceramics after 24h of interaction with artificial saliva

From examples 10 to 18, it can be seen that the microcrystalline glass powder obtained by heat-treating the bioactive glass powder significantly accelerates the generation rate of hydroxyapatite, and can precipitate a large amount of hydroxyapatite and Zn, Sn, Sr, and F after 24 hours of interaction with artificial saliva, which indicates that the microcrystalline glass powder provided in examples 10 to 18 not only has good bioactivity, but also can promote cell tissue growth and osteoblast differentiation, simultaneously can inhibit cancer cell growth, promote formation of protein and nucleic acid, is more beneficial to promoting human health and growth, can reduce the generation time of hydroxyapatite to 24 hours, and accelerate the treatment process.

As can be seen from comparative examples 12 to 21, when the bioactive glass powders provided in comparative examples 1 to 10 were subjected to heat treatment, they were subjected to crystal nucleation and crystal formation, and thus hydroxyapatite could not be formed, which indicates that Na₂The content of O is higher than 13%, and the microcrystalline glass with bioactivity cannot be obtained, so that the therapeutic effect cannot be achieved.

Test example 2

XRD tests are respectively carried out on the microcrystalline glass powder provided by the examples 10-13, 17-18 and the comparative examples 12-21, and the obtained spectrograms are shown in figures 1-4, wherein figure 1 is the XRD spectrogram of the microcrystalline glass provided by the examples 10-13; FIG. 2 is an XRD spectrum of the microcrystalline glass powder provided in comparative examples 12-15, and FIG. 3 is an XRD spectrum of the microcrystalline glass powder provided in comparative examples 16-17 and examples 17-18; FIG. 4 is an XRD spectrum of the microcrystalline glass powder provided in comparative examples 18-21.

As can be seen from FIG. 1, the microcrystalline glass powders provided in examples 10 to 13 were formed with CaSiO₃(wollastonite) Ca₁₀(PO₄)₆(OH)₂(hydroxyapatite) and NaAlSiO₄(albite) crystalline phase, in which CaSiO₃As a main crystal phase, Ca₁₀(PO₄)₆(OH)₂And NaAlSiO₄Is a secondary crystalline phase.

As can be seen from FIG. 2, the microcrystalline glass powders provided in comparative examples 12 to 15 were formed with Na₂Ca₄(PO₄)₂SiO₄Crystal phase, Ca is not formed₁₀(PO₄)₆(OH)₂And NaAlSiO₄A crystalline phase.

As can be seen from fig. 3, comparative examples 16 and 17 provide microcrystalline glass powders in which Na is formed₂Ca₄(PO₄)₂SiO₄And NaAlSiO₄Crystalline phase, Ca (PO) not formed₄)₆(OH)₂A crystalline phase; example 17 provides a microcrystalline glass powder having Ca formed therein₁₀(PO₄)₆(OH)₂And NaAlSiO₄A crystalline phase; example 18 provides a microcrystalline glass powder having Ca formed therein₁₀(PO₄)₆(OH)₂A crystalline phase.

As can be seen from fig. 4, comparative examples 18 and 19 provide microcrystalline glass powders in which Na is formed₄Ca₄(Si₆O₁₈) And NaAlSiO₄Crystal phase, Ca is not formed₁₀(PO₄)₆(OH)₂A crystalline phase; comparative example 20 provides a microcrystalline glass powder having Na formed therein₄Ca₄(Si₆O₁₈) And NaAlSiO₄Crystal phase, Ca is not formed₁₀(PO₄)₆(OH)₂A crystalline phase; comparative example 21 provides a microcrystalline glass powder having Na formed therein₂Ca₃Al₂(PO₄)₂(SiO₄)₂Crystal phase, Ca is not formed₁₀(PO₄)₆(OH)₂And NaAlSiO₄A crystalline phase.

The XRD spectra of the microcrystalline glass powder provided in examples 17-18 and Ca in the standard card₁₀(PO₄)₆(OH)₂The XRD patterns of (A) and (B) were compared as shown in FIG. 5, in which the dotted line represents Ca₁₀(PO₄)₆(OH)₂As shown in FIG. 5, Ca is formed in all the microcrystalline glass powders provided by 17-18 in the standard card spectrogram₁₀(PO₄)₆(OH)₂A crystalline phase.

Test example 3

DTA tests were performed on the crystallized glass powders provided in examples 10 to 13, and the DTA curves obtained are shown in FIG. 6.

As can be seen from FIG. 6, the microcrystalline glass powders provided in examples 10 to 13 exhibited endothermic peaks near 680 ℃, indicating that wollastonite (CaSiO) formation began near 680 ℃₃) Albite (NaAlSiO)₄) And hydroxyapatite (Ca)₁₀(PO₄)₆(OH)₂) A crystal nucleus of (1); an endothermic peak appears near 850 ℃, which indicates that crystal nuclei grow near 850 ℃, a crystal phase is generated, and the transition from the amorphous state to the glass-ceramic is completed.

Test example 4

The appearance and the appearance of the microcrystalline glass provided by the embodiments 10 to 13 are respectively observed, as shown in fig. 7(a) to 7(d), wherein fig. 7(a) is an appearance and appearance diagram of the microcrystalline glass provided by the embodiment 10; FIG. 7(b) is an appearance profile diagram of a glass ceramic provided in example 11; FIG. 7(c) is an appearance profile of a glass-ceramic provided in example 12; fig. 7(d) is an appearance profile diagram of the microcrystalline glass provided in example 13.

As can be seen from fig. 7(a) to 7(d), the crystallized glass powders provided in examples 10 to 13 all had a glossy milky white color.

Test example 5

Observing the microscopic appearances of the microcrystalline glass provided by 10-13 by adopting SEM respectively, as shown in FIGS. 8(a) -8 (d), wherein FIG. 8(a) is an SEM appearance image of the microcrystalline glass provided by example 10; fig. 8(b) is an SEM topography of the glass-ceramic provided in example 11; fig. 8(c) is an SEM topography of the glass-ceramic provided in example 12; fig. 8(d) is an SEM topography of the glass ceramics provided in example 13.

As can be seen from fig. 8(a) to 8(d), in the crystallized glass powders provided in examples 10 to 13, a plurality of small crystal grains were formed inside, and the plurality of crystal grains were agglomerated into large crystal grains, and the particle size of the large crystal grains was 100 to 200 nm.

(III) comparison of bioactive glass with microcrystalline glass

Test example 6

The bioactive glass powder provided in example 4 and the microcrystalline glass powder provided in example 13 were allowed to act on artificial saliva, and the bioactive glass powder provided in example 4 was taken out for 24h, 48h and 72h after being brought into contact with artificial saliva, respectively, and subjected to XRD measurement, and an XRD spectrum was plotted. The results are shown in FIG. 9; the microcrystalline glass provided in example 13 was taken out from the artificial saliva at 0h, 24h, 48h and 72h, respectively, and subjected to XRD measurement, and an XRD spectrum was plotted, with the result shown in fig. 10.

As can be seen from FIG. 9, the bioactive glass provided in example 4 did not have Ca for the first 48 hours₁₀(PO₄)₆(OH)₂Generation, Ca is generated only in 72h₁₀(PO₄)₆(OH)₂。

As can be seen from fig. 10, the microcrystalline glass powder provided in example 13 was formed with CaSiO at 0h₃And Ca₁₀(PO₄)₆(OH)₂At 24h, CaSiO₃All converted to Ca₁₀(PO₄)₆(OH)₂The XRD patterns at 48h and 72h were the same as those at 24h, which indicates CaSiO in the microcrystalline glass powder provided in example 15₃Complete conversion to Ca at 24h₁₀(PO₄)₆(OH)₂。

Test example 7

The bioactive glass powder provided in example 4 and the microcrystalline glass powder provided in example 13 were subjected to dissolution testing with artificial saliva, and the test results are shown in table 4.

TABLE 4 table of dissolution performance data of bioactive glass powder and microcrystalline glass powder

As can be seen from table 4, the bioactive glass powder provided in example 4 and the microcrystalline glass powder provided in example 13 have good dissolution properties, Zn, Sn, Sr, and F are significantly dissolved, and the dissolution properties of the respective components of the microcrystalline glass powder provided in example 13 are more excellent.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. The bioactive glass is characterized by comprising the following raw materials in percentage by mass: SiO 2₂ 50～55％、CaO 20～30％、P₂O₅ 5～12％、Na₂O 8～13％、ZnO 0.5～1.5％、SnO₂0.5-1.5%, SrO 0.5-1.5% and F0.5-1.5%;

the preparation method of the bioactive glass comprises the following steps: will be provided withSiO₂、CaO、P₂O₅、Na₂O、ZnO、SnO₂The SrO and the F are mixed uniformly, melted at the temperature of 1500-.

2. The bioactive glass of claim 1 wherein the bioactive glass is a bioactive glass powder.

3. The bioactive glass of claim 2 wherein the bioactive glass powder has a particle size of 300 to 500 mesh.

4. The bioactive glass of claim 1 wherein CaO and P are₂O₅The mass ratio of (A) to (B) is 2.5 to 4.

5. The bioactive glass of claim 1 wherein CaO and P are₂O₅The mass ratio of (A) to (B) is 3 to 4.

6. The bioactive glass of claim 1 wherein the Na is₂The content of O is 10-12.8%.

7. The bioactive glass of claim 1 wherein the Na is₂The content of O is 11.5-12.5%.

8. A glass-ceramic, characterized by being prepared from the bioactive glass according to any one of claims 1 to 7.

9. The glass-ceramic according to claim 8, wherein the glass-ceramic is a glass-ceramic powder.

10. The glass-ceramic according to claim 9, wherein the particle size of the glass-ceramic powder is 300 to 500 mesh.

11. The glass-ceramic according to claim 9, characterized in that it comprises wollastonite grains and hydroxyapatite grains.

12. The glass-ceramic according to claim 11, wherein the wollastonite crystal grain has a particle size of 100 to 200 nm.

13. The glass-ceramic according to claim 11, wherein the hydroxyapatite crystal grains have a particle size of 100 to 200 nm.

14. The method for producing a glass-ceramic according to any one of claims 8 to 13, characterized by comprising the steps of: and (3) carrying out heat treatment on the bioactive glass at the temperature of 600-900 ℃ for 3-7 h to obtain the glass ceramics.

15. The method of claim 14, wherein the bioactive glass is a bioactive glass powder.

16. The method of claim 15,

the particle size of the bioactive glass powder is 300-500 meshes.

17. The method according to claim 14, wherein the heat treatment comprises a crystallization nucleation stage and a crystallization growth stage, the temperature of the crystallization nucleation stage is 600-750 ℃ and the time is 1-3 h, and the temperature of the crystallization growth stage is 700-900 ℃ and the time is 2-4 h.

18. The preparation method according to claim 17, wherein the temperature of the crystallization nucleation stage is 650 to 710 ℃ for 1 to 2.5 hours, and the temperature of the crystallization growth stage is 760 to 850 ℃ for 2 to 3.5 hours.

19. Use of the bioactive glass according to any one of claims 1 to 7 or the microcrystalline glass according to any one of claims 8 to 13 in the preparation of a medicament or health product for oral diseases.