A ca-tisi-o5 glass, its preparation method and use

Abstract

The application discloses CaTiSiO5 glass and a preparation method and application thereof. The preparation method comprises the following steps: under a container-free gas suspension condition, a CaTiSiO5 ceramic preform is melted by using a laser to obtain a CaTiSiO5 melt; and the CaTiSiO5 melt is cooled to room temperature after being kept for a period of time, so that CaTiSiO5 glass is obtained. The CaTiSiO5 glass with a metastable amorphous phase is prepared from the CaTiSiO5 ceramic, the ion release rate and the in-vitro biological activity are improved, so that the prepared new CaTiSiO5 glass can provide a suitable ion release rate and a weak alkaline pH environment, and promote bone tissue repair.

Description

TECHNICAL FIELD

[0001] The application discloses CaTiSiO5 glass as well as a preparation method and application thereof, and belongs to the technical field of inorganic material preparation and biomaterials. BACKGROUND

[0002] Bioactive glass is widely used in the field of tissue engineering as a bone tissue scaffold material due to its good biocompatibility and bioactivity. A large amount of network modifiers such as alkali metals and alkaline earth metals are introduced into the bioactive glass 45S5 system used in clinical application, so that the stable bridging oxygen bond is changed into a high-activity non-bridging oxygen bond to form an open network structure. However, early excessive ion release easily causes the local pH value to increase too fast to reach 12-13, which affects the activity of enzymes and the cell metabolism process, leads to the decrease of osteoblast activity or even apoptosis, and causes non-bacterial inflammation or even repair failure.

[0003] The pH value plays a key role in bone remodeling. The acid-base degree of the in-vivo environment affects the balance of bone homeostasis by affecting the activity of osteoblasts and osteoclasts. A suitable alkaline environment can be conducive to the osteogenic differentiation of bone marrow mesenchymal stem cells, thereby increasing the number of osteoblasts, and can also significantly inhibit the surrounding active osteoclasts to create a good osteogenic microenvironment. However, an over-alkaline environment can promote the aging of osteoblasts and significantly inhibit the proliferation ability of osteoblasts. Therefore, it is an effective strategy to improve the osteogenic activity of implanted biomaterials by giving them a suitable alkalinity.

[0004] Titanite (CaTiSiO5) is a ternary system ceramic of calcium, silicon and titanium, belongs to monoclinic system, has excellent chemical stability and thermal stability, but the calcium and silicon ions with bioactivity contained therein are difficult to release because they exist in the form of [CaO7] and [SiO4] in the crystal structure. SUMMARY

[0005] In view of the problems in the prior art, the application provides a CaTiSiO5 glass as well as a preparation method and application thereof. The CaTiSiO5 ceramic is prepared into CaTiSiO5 glass with metastable amorphous phase, so as to improve the ion release rate and in-vitro bioactivity, thereby enabling the prepared new CaTiSiO5 glass to provide a suitable ion release rate and weak alkaline pH environment and promote bone tissue repair.

[0006] In a first aspect, the application provides a preparation method of CaTiSiO5 glass. The preparation method comprises: under container-free gas suspension conditions, using a laser to melt a CaTiSiO5 ceramic preform to obtain a CaTiSiO5 melt; and after heat preservation for a period of time, cooling the CaTiSiO5 melt to room temperature to obtain CaTiSiO5 glass.

[0007] Preferably, the power of the laser is ≤160W, and the wavelength of the laser is 800-1100nm.

[0008] Preferably, the melting temperature is 1400-1800℃, the holding time is 10-200s, and the cooling rate is 6-20℃ / s.

[0009] Preferably, the working atmosphere in the containerless gas suspension is oxygen, and the gas pressure is 0.2-1.5MPa.

[0010] Preferably, the CaTiSiO5 ceramic powder is synthesized by a sol-gel method and is formed into a CaTiSiO5 ceramic preform.

[0011] Preferably, the synthesis of the CaTiSiO5 ceramic powder by a sol-gel method comprises the following steps: uniformly stirring an acidic mixed solution containing an organic silicon source and a calcium source, then adding an organic titanium source, and continuing to stir until a sol is formed; the sol is subjected to gelation, drying, grinding, and calcination to obtain the CaTiSiO5 ceramic powder; preferably, the organic silicon source is tetraethyl orthosilicate and / or silica sol, the calcium source is calcium nitrate and / or its hydrate, and the organic titanium source is tetrabutyl titanate and / or tetraisopropyl titanate.

[0012] Preferably, the temperature for gelation is 50-70℃, and the time for gelation is 10-72h; the temperature for calcination is 1100-1150℃, and the time for calcination is 0.5-3h.

[0013] Preferably, a binder is added to the CaTiSiO5 ceramic powder, the mixture is subjected to press forming to obtain a ceramic green body, and the ceramic green body is subjected to normal pressure sintering to obtain the CaTiSiO5 ceramic preform; preferably, the temperature for sintering is 1200-1250℃, and the time for normal pressure sintering is 0.5-3h; more preferably, the binder is a polyvinyl alcohol binder and / or a resin binder; and the amount of the binder is 0.5-5wt% of the CaTiSiO5 ceramic powder.

[0014] In a second aspect, the present application provides a CaTiSiO5 glass obtained by the preparation method of any one of the above.

[0015] In a second aspect, the present application provides the use of the CaTiSiO5 glass of the above in the preparation of a bone repair material. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 are photographs of CaTiSiO5 ceramic prepared by a sol-gel method and CaTiSiO5 glass prepared by containerless gas suspension.

[0017] Figure 2 are an XRD pattern of CaTiSiO5 ceramic (A) and an XRD pattern of CaTiSiO5 glass (B).

[0018] Figure 3 is the surface scanning electron microscope image (A) and the element distribution energy spectrum area scanning image (B) of CaTiSiO5 glass.

[0019] Figure 4 is the surface micro-morphology image (A) and EDS component analysis (B) of CaTiSiO5 ceramic after mineralization for 14 days, the surface micro-morphology image (C) and EDS component analysis (D) of CaTiSiO5 glass after mineralization for 14 days. It shows that CaTiSiO5 glass has good in vitro mineralization activity.

[0020] Figure 5 is the XRD image of CaTiSiO5 ceramic and CaTiSiO5 glass after mineralization for 14 days.

[0021] Figure 6 is the pH change (A) and mass change (B) of CaTiSiO5 ceramic, CaTiSiO5 glass and 45S5 bioactive glass after immersion in Tris-HCl solution for different time, and the release behavior of Ca ions (C) and Si ions (D). Compared with traditional bioactive glass 45S5, CaTiSiO5 glass can provide a weak alkaline environment and a suitable Ca and Si ion environment.

[0022] Figure 7 is the influence of CaTiSiO5 ceramic, CaTiSiO5 glass and 45S5 on the proliferation of bone marrow mesenchymal stem cells (hBMSC) (A) and the expression of osteogenic genes BMP2 (B), OPN (C) and ALP (D). It shows that CaTiSiO5 glass can promote the proliferation of osteoblasts and promote the expression of osteogenic related genes.

[0023] Figure 8 is the influence of CaTiSiO5 ceramic, CaTiSiO5 glass and 45S5 on the expression of osteoclast genes NFATc1 (A), CTR (B), ACP5 (C) and MMP9 (D). It shows that CaTiSiO5 glass can inhibit the activity of osteoclasts.

[0024] Figure 9 is the photo of CaTiSiO5 glass obtained at different cooling rates. DETAILED DESCRIPTION

[0025] The present application is further illustrated by the following embodiments, which should be understood as merely illustrative of the present application, but not limiting the present application.

[0026] It is difficult to prepare homogeneous CaO-TiO2-SiO2 system glass by traditional melting method, which usually needs repeated melting and precise control of annealing process, and the prepared CaO-TiO2-SiO2 system glass is prone to phase separation, resulting in uneven composition. The application provides a novel preparation method of CaTiSiO5 glass, which is obtained by containerless gas suspension technology, which is first proposed and realized by the application.

[0027] The preparation method of the CaTiSiO5 glass comprises: pressing and sintering CaTiSiO5 ceramic powder to obtain a CaTiSiO5 ceramic preform; and using containerless gas suspension technology to heat the CaTiSiO5 ceramic preform to a molten state by laser, and then cooling after heat preservation for a period of time to obtain CaTiSiO5 glass. The CaTiSiO5 glass prepared by the method can provide a weak alkaline environment, promote osteoblast differentiation and inhibit osteoclast activity, which is beneficial to bone tissue repair. The preparation method of the CaTiSiO5 glass is exemplarily described below.

[0028] The method for preparing CaTiSiO5 ceramic powder is not limited, and a method commonly used in the art can be used. The CaTiSiO5 ceramic powder can be synthesized by sol-gel method. In some embodiments, the CaTiSiO5 ceramic powder synthesized by sol-gel method comprises the following steps: stirring an acidic mixed solution containing an organic silicon source and a calcium source, then adding an organic titanium source, and continuing to stir until a sol is formed; the sol is subjected to gelation, drying, grinding (which can also be ball milling), and calcination to obtain CaTiSiO5 ceramic powder. The organic silicon source includes but is not limited to tetraethyl orthosilicate and / or silica sol. The calcium source includes but is not limited to calcium nitrate and / or its hydrate. The silicon-calcium molar ratio of the organic silicon source and the calcium source can be 1:1. The organic titanium source includes but is not limited to tetrabutyl titanate and / or tetraisopropyl titanate. The silicon-titanium molar ratio of the organic silicon source and the organic titanium source can be 1:1. As an example but not limited to, the concentration of the organic silicon source in the acidic mixed solution is 0.1 g / mL to 0.5 g / mL. The pH of the acidic mixed solution can be 2 to 5.

[0029] As an example, the organic silicon source and water are mixed uniformly to obtain a mixed solution, the pH of the mixed solution is adjusted to 2 to 5, and the calcium source and the organic titanium source are added in sequence in the mixed solution after adjusting the pH, and stirred until a sol is formed. Since the organic titanium source is prone to hydrolysis, the addition sequence of the organic titanium source is preferably set after the calcium source. The sol is sequentially subjected to gelation (which can also be called aging), drying, grinding, and calcination to obtain CaTiSiO5 ceramic powder. The pH can be adjusted by HNO3.

[0030] As another example, the silicon source is added into the acid solution, and the silicon source is completely hydrolyzed. Then the calcium source is added. After the calcium source is completely dissolved, the silicon source is added dropwise, and the silicon source is continuously stirred to be completely hydrolyzed to form a sol. The sol is subjected to gelling (which can also be referred to as aging), drying, grinding, and calcination in sequence to obtain the CaTiSiO5 ceramic powder.

[0031] The gelling temperature can be 50-70°C, and the gelling time can be 10-72 h. The drying temperature can be 90-150°C, and the drying time can be 24-72 h. The ball milling speed and time can be changed according to actual needs. For example, the ball milling speed is 100-400 rpm, and the ball milling time is 3-6 h. The calcination temperature can be 1100-1150°C, and the calcination time can be 0.5-3 h.

[0032] The CaTiSiO5 ceramic preform is prepared. The CaTiSiO5 ceramic powder is pressed and sintered to prepare the CaTiSiO5 ceramic preform. The preform can be in a block form.

[0033] As an example, a binder is added into the CaTiSiO5 ceramic powder, and a ceramic green body is obtained by pressing. The binder includes but is not limited to a polyvinyl alcohol binder and / or a resin binder. The amount of the binder can be 0.5-5 wt% of the amount of the CaTiSiO5 ceramic powder. An aqueous polyvinyl alcohol solution can be used as the binder. The mass fraction of the aqueous polyvinyl alcohol solution can be 0.5-5%. The pressing mode can be dry pressing. For example, the dry pressing pressure is 2-200 MPa. The ceramic green body is sintered to obtain the CaTiSiO5 ceramic preform. The sintering mode can be atmospheric sintering. In some embodiments, the sintering temperature is 1200-1250°C, and the atmospheric sintering time is 0.5-3 h.

[0034] The CaTiSiO5 glass is prepared. The CaTiSiO5 ceramic preform is prepared into the CaTiSiO5 glass by using a containerless gas suspension technique. The containerless gas suspension technique can completely avoid the contact contamination of the material surface by the container, inhibit heterogeneous nucleation, obtain deep undercooling, and realize rapid solidification, so as to enable the glassification of materials with low glass forming ability. The stable titanite crystal phase can be converted into a metastable amorphous phase by the containerless gas suspension technique, so as to improve the ion release rate and the in-vitro bioactivity. In addition, the CaTiSiO5 glass prepared by the containerless gas suspension technique has a uniform composition distribution and high purity, and is suitable for use as a bone repair material.

[0035] The CaTiSiO5 ceramic preform prepared above is melted by laser under a containerless gas suspension condition to obtain a CaTiSiO5 melt. The CaTiSiO5 melt is kept for a period of time and then cooled to room temperature to obtain a CaTiSiO5 glass. If the CaTiSiO5 ceramic preform is in the form of a block, the obtained CaTiSiO5 glass is in the form of a sphere. The above preparation can be carried out using a containerless gas suspension furnace (gas suspension heating furnace). The throat diameter of the nozzle of the containerless gas suspension furnace can affect the diameter of the CaTiSiO5 glass. The throat diameter of the nozzle of the containerless gas suspension furnace is 1-4 mm, and CaTiSiO5 glass spheres with a diameter of 2-5 mm can be prepared. The working atmosphere of the containerless gas suspension is oxygen, and the gas pressure is 0.2-1.5 MPa, preferably 0.3-1 MPa. The oxygen atmosphere can inhibit the loss of oxygen of TiO2 during cooling. The wavelength of the laser is 800-1100 nm, preferably 1064 nm. The power of the laser is ≤160 W. Preferably, the power of the laser is 30-90 W. Controlling the power and wavelength of the laser within the above ranges can control the melting temperature within a suitable range (e.g., 1400-1800°C). The melting temperature is 1400-1800°C, preferably 1500°C. The holding time is 10-200 seconds, preferably 30-120 seconds, more preferably 30-60 seconds. Controlling the melting temperature and holding time within the above ranges can ensure that the ceramic block is fully melted to form a melt with uniform composition.

[0036] Using the containerless gas suspension technology can make the melt deeply undercooled to achieve rapid solidification. Generally, the extremely rapid cooling is achieved by directly turning off the laser, and the cooling rate can reach 200-300°C / s, and the material with low glass forming ability is vitrified. The cooling rate for preparing the CaTiSiO5 glass of the present application is controlled within 6-20°C / s. The cooling rate is very important for the composition and properties of the CaTiSiO5 glass. If the cooling rate is too slow (<6°C / s), phase separation is easy to occur, leading to heterogeneous nucleation and the precipitation of crystals, resulting in uneven phases of the prepared CaTiSiO5 glass. If the cooling rate is too fast (>20°C / s), TiO2 will produce defects due to loss of oxygen, and the transparency of the CaTiSiO5 glass will be poor.

[0037] The process of laser heating and cooling can also be repeated multiple times to remove bubbles in the melt.

[0038] The current silicon-based bioactive glass has problems of too fast ion release rate and too strong alkalinity. The CaTiSiO5 glass is amorphous in nature. The composition of the CaTiSiO5 glass is CaO:TiO2:SiO2=1:1:1. The new titanate bioactive glass (CaTiSiO5 glass) prepared by the method has suitable degradation performance and excellent mineralization performance, and can provide a suitable ion release rate and a mild weak alkaline environment to promote bone tissue repair.

[0039] The following further illustrates the embodiments to further illustrate the present application. It should also be understood that the following embodiments are only used to further illustrate the present application, and cannot be understood as limiting the protection scope of the present application. Some non-essential improvements and adjustments made by those skilled in the art according to the above content of the present application all belong to the protection scope of the present application. The specific process parameters in the following examples are only one example in the appropriate range, that is, those skilled in the art can select within the appropriate range through the description herein, and are not limited to the specific values in the following examples.

[0040] Example 1

[0041] Under stirring, 60 mL of 2M HNO3 and 100 mL of H2O are mixed to form an acid solution. 35.73 g of tetraethyl orthosilicate (Si(OC2H5)4) is added to the acid solution. After the complete hydrolysis of the tetraethyl orthosilicate, 40.50 g of calcium nitrate tetrahydrate is added. After the complete dissolution of the calcium nitrate tetrahydrate, tetrabutyl titanate (C 16 H 36 O4Ti) is added dropwise, and stirring is continued to completely hydrolyze the tetrabutyl titanate to form a white gel. The silicon-calcium-titanium molar ratio of the tetraethyl orthosilicate: calcium nitrate tetrahydrate: tetrabutyl titanate is 1:1:1. The white gel is aged at 60°C for 48 h and dried at 100°C for 48 h to obtain a dry gel. The dry gel is ground and calcined at 1100°C for 2 h to obtain a white powder. 5 g of the white powder is mixed with 0.1 g of a polyvinyl alcohol aqueous solution with a mass fraction of 5% as a binder to obtain a mixture to be formed. 0.25 g of the mixture to be formed is pressed into a round sheet with a diameter of 6 mm under a pressure of 30 MPa, and sintered at 1250°C for 2 h to obtain a CaTiSiO5 ceramic sheet.

[0042] The obtained CaTiSiO5 ceramic sheet is placed in a gas suspension heating furnace, oxygen is introduced, laser heating is performed, and the CaTiSiO5 glass is obtained by melting and heating at 1500°C for 30 seconds and cooling after the laser is turned off. The oxygen pressure is 0.6 MPa, the laser wavelength is 1064 nm, the laser power is 60 W, and the cooling rate is 20°C / s.

[0043] Figure 1is CaTiSiO5 ceramic prepared by sol-gel method and CaTiSiO5 glass prepared by containerless air suspension. It can be seen that the prepared CaTiSiO5 glass is colorless and transparent.

[0044] Figure 2 is XRD pattern of CaTiSiO5 ceramic (A) and XRD pattern of CaTiSiO5 glass (B). It can be seen that the prepared CaTiSiO5 ceramic phase is high-purity crystal phase, and the prepared CaTiSiO5 glass is amorphous phase.

[0045] Figure 3 is surface scanning electron microscope pattern (A) and element distribution energy spectrum area scanning pattern (B) of CaTiSiO5 glass. It can be seen that the CaTiSiO5 glass has uniform composition distribution and no phase separation.

[0046] Example 2

[0047] The in vitro induced mineralization performance of the material is evaluated by the method of soaking in simulated body fluid. The simulated body fluid is prepared according to the formula shown in Table 1, and the pH is adjusted to 7.4 by 1M HCl and Tris buffer. The CaTiSiO5 ceramic and CaTiSiO5 glass are respectively soaked in the simulated body fluid, and the liquid is changed every other day. After 14 days, the surface formation of hydroxyapatite is observed.

[0048] Table 1 Preparation scheme of simulated body fluid (1L)

[0049]

[0050] Figure 4 is surface micro-morphology and EDS composition analysis of CaTiSiO5 ceramic after 14 days of mineralization (A-B) and surface micro-morphology and EDS composition analysis of CaTiSiO5 glass after 14 days of mineralization (C-D). It can be seen that rod-shaped deposits are formed on the surface of CaTiSiO5 glass, and the calcium-phosphorus ratio is about 1.5, indicating that CaTiSiO5 glass has good ability to induce the formation of hydroxyapatite.

[0051] Figure 5 is XRD analysis of CaTiSiO5 ceramic and CaTiSiO5 glass after 14 days of mineralization. It shows that the deposits on the surface of CaTiSiO5 glass are hydroxyapatite, indicating that CaTiSiO5 glass has good in vitro mineralization activity.

[0052] Example 3

[0053] The pH change, mass change and ion release change of CaTiSi05 ceramic, CaTiSi05 glass and 45S5 glass were evaluated by the method of block immersion in Tris-HCl (Tris-Hydroxymethyl aminomethane-Hydrochloric acid) before and after pH change. First, the weight of CaTiSi05 ceramic and CaTiSi05 glass and 45S5 glass before immersion was weighed (marked as m0), and then the Tris-HCl buffer solution with pH 7.4 was prepared at 37°C. Then, the block sample was placed in a centrifuge tube, the volume ratio of Tris-HCl buffer solution to block mass was controlled at about 200 mL / g, and the sample was placed in a 37°C shaking table at a speed of 120 rpm. The degradation performance test group set 1 day, 3 days, 7 days, 14 days and 28 days five time points, each group of three parallel samples. After reaching the preset time, the block sample was taken out, the Tris-HCl liquid was collected to test the pH value and the concentration of Ca and Si ions therein, and after washing with deionized water, it was dried in a 60°C oven for 24h, and the mass after immersion (mt) was weighed. The degradation rate of the block sample was calculated by the following formula: degradation rate=(mt-m0) / m0.

[0054] Figure 6 Figure 1 is the pH change (A) and mass change (B) and the release behavior of Ca ions (C) and Si ions (D) of CaTiSi05 ceramic, CaTiSi05 glass and 45S5 bioactive glass immersed in Tris-HCl solution for different times. It can be seen that compared with 45S5, the ion release rate and pH value of CaTiSi05 glass are greatly reduced. Compared with CaTiSi05 ceramic, CaTiSi05 glass has high solubility and fast ion release rate. Compared with the traditional bioactive glass 45S5, CaTiSi05 glass can provide a weak alkaline environment and a suitable Ca and Si ion environment.

[0055] Example 4

[0056] The effect of CaTiSi05 ceramic, CaTiSi05 glass and 45S5 glass on the proliferation of hBMSC was investigated by direct contact co-culture. After sterilization of the material at high temperature, human hBMSC were inoculated on the surface of the block sample at a density of 5000 cells per well, and cultured in an incubator for 1, 3 and 5 days, with liquid exchange every other day. After reaching the preset time, the cell activity was detected by CCK8 (Cell Counting Kit) kit. Real-time fluorescence quantitative (PCR) method was used to study the expression of hBMSC osteogenesis related genes BMP2, OPN and ALP in CaTiSi05 ceramic, CaTiSi05 glass and 45S5 glass.

[0057] Figure 7Effect of CaTiSiO5 ceramic, CaTiSiO5 glass and 45S5 on proliferation of bone marrow mesenchymal stem cells (hBMSC) (A) and expression of osteogenic genes BMP2 (B), OPN (C) and ALP (D). It can be seen that CaTiSiO5 glass can promote osteoblast proliferation and promote expression of osteogenic related genes.

[0058] Example 5

[0059] Mouse bone marrow-derived macrophages (BMDMs) were used to evaluate the effect of CaTiSiO5 ceramic, CaTiSiO5 glass and 45S5 glass on osteoclast activity. The materials were placed in a 96-well plate, and BMDMs were seeded at a density of 2 x 10 3 When the cells adhered, the osteoclast differentiation complete medium (αMEM base medium, 30 ng / mL RANKL, 50 ng / mL M-CSF) was replaced, and the cells were cultured for 7 days. Total RNA was extracted using Trizol reagent, cDNA was synthesized according to the reverse transcription kit instructions (TAKARA RR036A), and TB Green kit (TAKARA RR420A) was used to analyze osteoclast related genes (MMP9, NFATc1, CTR and ACP5) in a StepOnePlus fluorescence quantitative PCR instrument.

[0060] Figure 8 Effect of CaTiSiO5 ceramic, CaTiSiO5 glass and 45S5 on expression of osteoclast genes NFATc1 (A), CTR (B), ACP5 (C) and MMP9 (D). It can be seen that CaTiSiO5 glass can inhibit osteoclast activity.

[0061] Comparative Example 1

[0062] The same as Example 1, except that the cooling rate was 5°C / s, 10°C / s, 200°C / s. Figure 9 Photos of CaTiSiO5 glass obtained at different cooling rates. It can be seen that when the cooling rate is too fast, TiO2 will be defective due to oxygen loss, resulting in black CaTiSiO5 glass; when the cooling rate is too slow, CaTiSiO5 glass is prone to crystallization during preparation.

Claims

1. A method for preparing CaTiSiO5 transparent glass, characterized in that, The preparation method includes: synthesizing CaTiSiO5 ceramic powder by sol-gel method and shaping it into CaTiSiO5 ceramic preform; melting the CaTiSiO5 ceramic preform with laser under containerless air suspension conditions to obtain CaTiSiO5 melt; holding the CaTiSiO5 melt at a certain temperature for a period of time and then cooling it to room temperature to obtain CaTiSiO5 transparent glass; wherein, the melting temperature is 1400-1800℃, the holding time is 10-200 seconds, and the cooling rate is 6-20℃ / second.

2. The preparation method according to claim 1, characterized in that, The laser power is ≤ 160W and the laser wavelength is 800~1100nm.

3. The preparation method according to claim 1, characterized in that, The working atmosphere for containerless air suspension is oxygen, with a pressure of 0.2–1.5 MPa.

4. The preparation method according to claim 1, characterized in that, The synthesis of CaTiSiO5 ceramic powder by the sol-gel method includes the following steps: stirring an acidic mixture containing an organosilicon source and a calcium source until homogeneous, then adding an organotitanium source and continuing to stir until a sol is formed; the sol is then gelled, dried, ground, and calcined to obtain CaTiSiO5 ceramic powder.

5. The preparation method according to claim 4, characterized in that, The organosilicon source is tetraethyl orthosilicate and / or silica sol, the calcium source is calcium nitrate and / or its hydrate, and the organotitanium source is tetrabutyl titanate and / or tetraisopropyl titanate.

6. The preparation method according to claim 4, characterized in that, The gelation temperature is 50–70℃, and the gelation time is 10–72 h; the calcination temperature is 1100–1150℃, and the calcination time is 0.5–3 h.

7. The preparation method according to claim 1, characterized in that, A binder is added to CaTiSiO5 ceramic powder, and the powder is pressed to obtain a ceramic green body. The ceramic green body is then sintered under normal pressure to obtain a CaTiSiO5 ceramic preform.

8. The preparation method according to claim 7, characterized in that, The sintering temperature is 1200-1250℃, and the sintering time under normal pressure is 0.5-3h; the binder is polyvinyl alcohol binder and / or resin binder; the amount of binder is 0.5-5wt% of CaTiSiO5 ceramic powder.

9. The application of the CaTiSiO5 transparent glass obtained by the preparation method according to any one of claims 1 to 8 in the preparation of bone repair materials.

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