CN111773432A - Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and its preparation and application - Google Patents

Abstract

The invention discloses a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high biological activity, comprising: a composite filler obtained by uniformly mixing composite calcium phosphate/calcium silicate and magnesium-based amorphous powder/fiber Solid phase substance, and solidified liquid obtained by dissolving hydrogen phosphate in water. The invention also discloses a preparation method and application of an injectable magnesium-based amorphous-calcium phosphate/calcium silicate bone cement and a solid filling block. Bioactive injectable magnesium-based amorphous-calcium phosphate/calcium silicate bone cement for preparing injectable products for bone tissue wound repair; curing and drying the bone cement in vitro to form a bulk filler for use in Filling of open bone defects. The present invention has low cost of raw materials, simple preparation method, and the obtained magnesium-based amorphous-calcium phosphate/calcium silicate composite filler has high biological activity, and can form a porous structure in the body, which is beneficial to tissue repair.

Description

Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and its preparation and application

technical field

The invention belongs to the technical field of preparation of medical bone filling materials, and in particular provides a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high biological activity and a preparation method and application thereof.

Background technique

Clinically, bone defects caused by bone tumors, orthopedic deformities of the limbs and spine, severe bone trauma, osteoporosis, and osteonecrosis need to be reconstructed and treated by bone transplantation. However, due to the limited source of autologous bone, increased surgical trauma, and the risk of immune response and disease transmission of allogeneic bone, its clinical application is limited. Artificial bone implant materials have always been the focus of bone tissue research and are expected to be used to replace autologous or allogeneic bone. High porosity, degradability, high initial mechanical properties and good biological activity are the basic conditions that bone repair materials must meet.

Calcium sulfate has been used in bone replacement materials for over 100 years and has been shown to be safe and biocompatible. In 1980, Coetzee et al. used calcium sulfate in 110 cases of skull and facial bone defects, and he concluded that calcium sulfate is an excellent bone graft substitute, even comparable to its own bone graft. Later, calcium sulfate was criticized for degrading before new bone was completely grown in, so calcium sulfate was used as a bone filler material, and its degradation rate was too fast. Therefore, calcium phosphate was used as a filler for bone defects, and the development of Injectable calcium phosphate bone cement. Calcium phosphate cement (calcium phosphate cement, CPC), also known as hydroxyapatite cement (HAC), is a kind of self-fixing non-ceramic hydroxyapatite artificial bone first developed by Brown and Chow. bone material. It has become a new type of bone tissue repair and replacement material because of its good biocompatibility, osteoconductivity, biosafety, arbitrary shaping, and isothermal properties during the curing process. Widely concerned, it has become one of the hot spots in the field of clinical tissue repair research and application. CPC is made of two raw materials, solid phase and liquid phase, in a certain proportion, mixed into a paste, and then implanted into the body, and crystallizes and solidifies by itself in the in vivo environment. The chemical composition of the final product after curing is similar to the inorganic composition of bone tissue, and its crystal phase structure is also similar to that of bone tissue. After implantation in the bone defect, it can be gradually degraded and absorbed, and the calcium and phosphorus released from the degradation participate in the formation of bone tissue in the defect area. The compressive strength of the final product of CPC is 36-55MPa, which is between the cancellous bone and the bone cortex. The size of the compressive strength is closely related to the particle size of the solid phase components used in the CPC curing process, the porosity of the final product and the crystallinity of HA, and the porosity of the final product is directly related to the powder-to-liquid ratio during blending. CPC with larger compressive strength is suitable for the repair of bone defects in low weight-bearing parts, and CPC with smaller compressive strength is suitable for the repair of bone defects in non-weight-bearing parts or small bone defects and root canal filling. However, the biological activity of CPC still needs to be improved in order to achieve better bone repair effect. Compared with calcium phosphate materials, calcium silicate (CS)-based materials have excellent biological activities and have also received increasing attention in recent years. A large number of studies have proved that CS-based materials can quickly form apatite deposits through the release of Si ions, which can promote the formation and reconstruction of bone tissue. Self-curing CS bone cement has the advantage of low self-curing time, and exhibits good osteoconductivity and inhibition of inflammation in human dental pulp cells.

However, the common problems of CPC and CS are that although they also have a certain porosity, due to the nanoscale or submicron pore scale, there is a lack of large pores to promote bone tissue growth, and not only can bone cells not grow into , even the tissue fluid is difficult to penetrate, and it is difficult to exert its osteoconductive effect; moreover, compared with the growth rate of bone tissue, the degradation rate of the two is too low, especially calcium silicate bone cement, the degradation and absorption process of the material in the body is gradually Therefore, the absorption rate is low and the degradation is slow, which hinders the formation and reconstruction of new bone tissue; in addition, the bioactivity of the two depends on the bioactive ions generated by the degradation of their own materials to a large extent, in addition to the osteoconduction effect. , and the low degradation rate of the two makes the biological activity insufficient to meet the clinical needs, especially in the early stage of implantation, the biological activity is lower.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the above calcium phosphate/calcium silicate bone cement, the present invention provides a calcium phosphate/calcium silicate bone cement with high biological activity and can be degraded into pores in vivo and a method for preparing a bulk filler. According to the characteristics of magnesium-based amorphous metal material in vivo degradation rate is faster than calcium phosphate bone cement material, and the degradation produces magnesium ions with high biological activity, and the hydrogen is released at the same time, the magnesium-based amorphous metal powder/fiber is degraded in the present invention. It is compounded with calcium phosphate/calcium silicate powder, and the self-curing characteristics of calcium phosphate/calcium silicate are used to prepare a compound with higher biological activity, which can be degraded into pores in vivo, and the later degradation speed is fast, which is conducive to the growth of new bone tissue. New bone cement and block filling material. In addition, since the degradation rate of magnesium-based amorphous alloys in vivo is lower than that of crystalline magnesium and its alloys, it can be ensured that during the preparation process of composite materials, the long solidification time of composite materials caused by the rapid degradation of magnesium and its alloys can be avoided. The problem of premature collapse in the body.

The technical scheme adopted in the present invention is as follows:

A magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high biological activity, characterized in that: magnesium-based amorphous powder/fiber is added to the injectable calcium phosphate/calcium silicate filler to form a composite filler .

As the preferred technical solution:

The magnesium-based amorphous composition is MgZnCaSr, wherein the Zn content is: 21-40 at.%, the Ca content is: 2-7 at.%, the Sr content is: 0-5 at.%, and the balance of Mg.

The magnesium-based amorphous powder/fiber content accounts for 1-30wt.% of the composite filler

The magnesium-based amorphous powder is spherical or irregular, and the particle size is less than 1 mm.

The magnesium-based amorphous fibers are 1-30 mm long and 0.1-1 mm wide.

The present invention also provides a method for preparing the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler, which is characterized in that it includes the following steps:

(1) mixing calcium phosphate/calcium silicate bone cement solid phase powder with magnesium-based amorphous powder/fiber to obtain solid phase composite powder;

(2) Prepare a buffer solution of equimolar concentration of 0.2-1.0 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate with analytically pure or higher-grade sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water or distilled water as a solidifying liquid;

(3) preparing the solid-phase composite powder prepared in step (1) and the solidifying liquid prepared in step (2) according to a solid-liquid ratio (0.1-3):1 to prepare a composite bone cement slurry, and the prepared bone cement slurry The material can be directly injected into the bone defect site with a syringe for use.

(4) injecting the bone cement slurry prepared in step (3) into a mold to solidify for 20 minutes to 6 hours, and then drying at 80 to 100° C. to prepare a bulk filling material for filling and treating open bone defects.

The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method of the invention can be reconciled to form a paste, and a highly biologically active injectable magnesium-based amorphous-calcium phosphate/calcium silicate bone cement can be obtained , for the preparation of injectable products for bone tissue wound repair.

The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method of the invention can be cured and dried in vitro after being mixed to form a paste, to form a block filler, which is used for open bone Filling of defects.

Calcium phosphate/calcium silicate bone cement degrades slowly, while magnesium-based amorphous powder/fiber degrades faster than the two, and the degradation produces magnesium ions with high biological activity, which can play an osteoinductive effect and further enhance calcium phosphate/silicic acid. The biological activity of calcium, especially in the early stage of implantation, calcium phosphate/calcium silicate cannot exert biological activity due to the slow degradation rate, while magnesium-based amorphous powder/fiber degrades fast and can effectively exert osteoinductive effect in the initial stage. Promote the initial bone healing, and form an effective complement to the time when calcium phosphate/calcium silicate plays a role in biological activity;

The vacancies left by the degradation of magnesium-based amorphous powder/fiber and the hydrogen generated by the degradation can play a role in pore formation, and bone cells can grow in the pores, which is conducive to the vascularization of the material, and ensures the supply of nutrients to the internal tissues of the material, thereby promoting The growth of new bone tissue and the reconstruction of autologous bone; at the same time, the degradation of magnesium-based amorphous powder/fiber will increase the surface area of calcium phosphate/calcium silicate in contact with body fluids, and increase the degradation rate of the implant in the later stage.

In addition, since the degradation rate of magnesium-based amorphous alloys in vivo is lower than that of crystalline magnesium and its alloys, it can be ensured that during the preparation process of composite materials, the long solidification time of composite materials due to the rapid degradation of magnesium and its alloys can be avoided. The problem of premature collapse in the body.

The invention has low raw material cost, simple preparation method, and the obtained magnesium-based amorphous-calcium phosphate/calcium silicate composite filler product has high biological activity, and can form a porous structure in the body, which is beneficial to tissue repair, and is mainly used for bone repair. Defect repair and bone tissue engineering scaffold materials, can also be used as dental restoration materials. When in use, the prepared slurry can be directly injected into the bone defect with a syringe, or the slurry can be injected into a mold to solidify and form, and then implanted into the bone defect.

Description of drawings

Figure 1 is a photo of MgZnCa magnesium-based amorphous powder-calcium phosphate composite bone cement.

Figure 2 shows a large number of visible pores on the surface of the MgZnCa magnesium-based amorphous powder-calcium phosphate composite bone cement after curing and soaking in simulated body fluid for 24 hours.

Figure 3 is a macro photo of calcium phosphate bone cement and Mg ₆₉ Zn ₂₆ Ca ₅ magnesium-based amorphous powder-calcium phosphate composite bone cement before soaking in simulated body fluids and after soaking for 7 days and 14 days, in which calcium phosphate bone cement: before soaking (a), soaking for 7 days (b) and soaking for 14 days (c); Mg ₆₉ Zn ₂₆ Ca ₅ magnesium-based amorphous powder-calcium phosphate composite bone cement: before soaking d), soaking for 7 days (e) and soaking for 14 days day(f).

Detailed ways

The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

Example 1

Mix α-tricalcium phosphate powder with Mg ₆₉ Zn ₂₆ Ca ₅ magnesium-based amorphous powder (spherical, with a particle size of 0.5 mm), wherein the Mg ₆₉ Zn ₂₆ Ca ₅ magnesium-based amorphous powder accounts for 5% by weight; Analytical pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water were used to prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration buffer solution as solidifying liquid; The solid-liquid ratio is 0.3:1 to prepare the composite bone cement slurry. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use.

In vitro experiments confirmed that the magnesium-calcium phosphate composite bone cement has good injectability (as shown in Figure 1) and self-curing properties. It shows that in the early stage of soaking, the magnesium-based amorphous powder in the composite bone cement begins to degrade, and a large number of holes are formed in the bone cement, which can provide favorable conditions for the growth of the surrounding bone tissue. Figure 3 is the macrophotograph of calcium phosphate bone cement and MgZnCa magnesium-based amorphous powder-calcium phosphate composite bone cement before soaking in simulated body fluids and after soaking for 7 days and 14 days. It can be seen from the figure that the Mg ₆₉ Zn ₂₆ Ca ₅ magnesium-based amorphous powder-calcium phosphate composite bone cement still maintains a complete structure after soaking for 14 days, while the calcium phosphate bone cement has collapsed and fractured. It can be seen that the Mg ₆₉ Zn ₂₆ The Ca ₅ magnesium-based amorphous powder-calcium phosphate composite bone cement has excellent anti-collapse properties.

Example 2

Mix α-tricalcium phosphate powder with Mg ₆₇ Zn ₂₈ Ca ₄ Sr ₁ magnesium-based amorphous powder (spherical, with a particle size of 0.5 mm), wherein the weight ratio of Mg ₆₇ Zn ₂₈ Ca ₄ Sr ₁ magnesium-based amorphous powder is 5%; use analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water to prepare a buffer solution of equimolar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate of 0.5 molar concentration as a solidification solution; compound the prepared solid phase The powder and the prepared solidifying liquid are prepared according to the solid-liquid ratio of 0.4:1 to prepare the composite bone cement slurry. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use. The above-prepared bone cement slurry is injected into a mold to solidify for 2.1 hours, and then dried at 80-100° C. to prepare a bulk filling material for filling and treating open bone defects.

Animal experiments confirmed that compared with the α-tricalcium phosphate bulk filler without Mg ₆₇ Zn ₂₈ Ca ₄ Sr ₁ magnesium-based amorphous powder, Mg ₆₇ Zn ₂₈ Ca ₄ Sr ₁ magnesium-based amorphous-calcium phosphate composite bulk The degradation cycle of the filler was significantly shorter, and due to the degradation of magnesium, the bone tissue grew into the magnesium-calcium phosphate composite bulk filler, showing high biological activity.

Example 3

Mix α-tricalcium phosphate powder with Mg ₆₅ Zn ₃₀ Ca ₄ Sr ₁ magnesium-based amorphous powder (irregular shape, maximum size is 1mm), wherein Mg ₆₅ Zn ₃₀ Ca ₄ Sr ₁ magnesium-based amorphous powder accounts for the weight ratio 5%; use analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water to prepare a buffer solution of 1.0 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration as a solidification solution; the prepared solid phase The composite powder and the prepared solidifying liquid are prepared according to the solid-liquid ratio of 1:1 to prepare the composite bone cement slurry. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use. The above-prepared bone cement slurry is injected into a mold to solidify for 30 minutes, and then dried at 80-100° C. to prepare a bulk filling material for filling and treating open bone defects.

Animal experiments confirmed that compared with the α-tricalcium phosphate bulk filler without Mg ₆₅ Zn ₃₀ Ca ₄ Sr ₁ magnesium-based amorphous powder, Mg ₆₅ Zn ₃₀ Ca ₄ Sr ₁ magnesium-based amorphous-calcium phosphate composite bulk The repair speed of cortical bone with filler is significantly accelerated.

Example 4

Mix β-tricalcium phosphate (β-TCP) powder with Mg ₇₀ Zn ₂₆ Ca ₂ Sr ₂ magnesium-based amorphous powder (irregular shape, maximum size 1mm), wherein Mg ₇₀ Zn ₂₆ Ca ₂ Sr ₂ magnesium-based non-crystalline powder The crystal powder accounts for 10% by weight; use analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water to prepare a buffer solution of 1.0 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration as the solidification liquid; The prepared solid-phase composite powder and the prepared solidification liquid are prepared according to a solid-liquid ratio of 0.7:1 to prepare a composite bone cement slurry. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use.

Animal experiments confirmed that, compared with the β-tricalcium phosphate bone cement without Mg ₇₀ Zn ₂₆ Ca ₂ Sr ₂ magnesium-based amorphous powder, the degradation rate of the bone cement after compounding was accelerated, and holes appeared, and the repair rate of cortical bone was significantly accelerated.

Example 5

Mix β-tricalcium phosphate (β-TCP) powder with Mg ₇₀ Zn ₂₆ Ca ₄ magnesium-based amorphous powder (spherical, with a particle size of 0.3 mm), wherein Mg ₇₀ Zn ₂₆ Ca ₄ magnesium-based amorphous powder accounts for the weight ratio 20%; use analytically pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water to prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration buffer solution as solidification liquid; prepare solid phase The composite powder and the prepared solidifying liquid are prepared according to the solid-liquid ratio of 2.5:1 to prepare the composite bone cement slurry. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use.

In vitro experiments confirmed that the Mg ₇₀ Zn ₂₆ Ca ₄ magnesium-based amorphous-β-TCP composite bone cement has good injectability and self-curing properties. It shows that in the early stage of soaking, the Mg ₇₀ Zn ₂₆ Ca ₄ amorphous powder in the composite bone cement begins to degrade, and a large number of holes are formed in the bone cement, which can provide favorable conditions for the ingrowth of the surrounding bone tissue.

Example 6

Mix the Mg ₆₈ Zn ₂₆ Ca ₁ Sr ₅ amorphous fibers (length 10mm, width 0.8mm) with α-tricalcium phosphate powder, wherein the Mg ₆₈ Zn ₂₆ Ca ₁ Sr ₅ amorphous fibers account for 20% by weight; Pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water are used to prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration buffer solution as solidification liquid; The composite bone cement slurry was prepared according to the solid-liquid ratio of 3:1. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use. The above-prepared bone cement slurry is injected into a mold to solidify for 2 hours, and then dried at 80-100° C. to prepare a bulk filling material for filling and treating open bone defects.

Animal experiments confirmed that the degradation cycle of the Mg ₆₈ Zn ₂₆ Ca ₁ Sr ₅ amorphous fiber-α-tricalcium phosphate composite bulk filler was significantly shorter than that of the α-tricalcium phosphate bulk filler without MgZnCa amorphous fibers. short, and due to the degradation of MgZnCa amorphous fibers, bone tissue grew into the interior of the Mg ₆₈ Zn ₂₆ Ca ₁ Sr ₅ amorphous fibers-α-tricalcium phosphate composite bulk filler, showing high biological activity.

Example 7

Mix Mg ₆₇ Zn ₃₀ Ca ₃ amorphous fibers (length 15mm, width 1.0mm) with β-tricalcium phosphate powder, wherein Mg ₆₇ Zn ₃₀ Ca ₃ fibers account for 30% by weight; use analytically pure sodium dihydrogen phosphate, Disodium hydrogen phosphate reagent and deionized water to prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate buffer solution with equimolar concentration as solidified liquid; : 1 to prepare composite bone cement slurry. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use.

Animal experiments confirmed that, compared with β-tricalcium phosphate cement without Mg ₆₇ Zn ₃₀ Ca ₃ amorphous fiber, the repair speed of Mg ₆₇ Zn ₃₀ Ca ₃ amorphous fiber-β-tricalcium phosphate composite bone cement on cortical bone Noticeably faster.

Example 8

Mix Mg ₆₆ Zn ₃₀ Ca ₂ Sr ₂ amorphous fibers (length 5mm, width 0.5mm) with β-tricalcium phosphate powder, wherein Mg ₆₆ Zn ₃₀ Ca ₂ Sr ₂ amorphous fibers account for 30% by weight; Pure sodium dihydrogen phosphate, disodium hydrogen phosphate reagent and deionized water are used to prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration buffer solution as solidification liquid; The composite bone cement slurry was prepared according to the solid-liquid ratio of 1:1. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use. The above-prepared bone cement slurry is injected into a mold to solidify for 1.2 hours, and then dried at 80-100° C. to prepare a bulk filling material for filling and treating open bone defects.

Animal experiments confirmed that, compared with the β-tricalcium phosphate bulk filling material without the addition of Mg ₆₆ Zn ₃₀ Ca ₂ Sr ₂ amorphous fibers, the degradation rate of the bulk filling material after compounding was accelerated, holes appeared on the surface, and the repair speed of cortical bone was obvious. accelerate.

Example 9

Mix Mg ₆₄ Zn ₃₀ Ca ₃ Sr ₃ amorphous fibers (length 7mm, width 0.5mm) with calcium silicate powder, wherein Mg ₆₄ Zn ₃₀ Ca ₃ Sr ₃ amorphous fibers account for 5% by weight; use analytically pure phosphoric acid Sodium dihydrogen, disodium hydrogen phosphate reagent and deionized water prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration buffer solution as solidified liquid; The composite bone cement slurry was prepared with a solid-liquid ratio of 0.5:1. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use.

Animal experiments confirmed that, compared with calcium silicate cement without Mg ₆₄ Zn ₃₀ Ca ₃ Sr ₃ amorphous fibers, the degradation rate of bone cement after compounding was accelerated, holes appeared on the surface, and the repair rate of cortical bone was significantly accelerated.

Example 10

Mix Mg ₆₄ Zn ₃₀ Ca ₁ Sr ₅ amorphous fiber (length 3mm, width 0.2mm) with calcium silicate powder, wherein Mg ₆₄ Zn ₃₀ Ca ₁ Sr ₅ amorphous fiber accounts for 5% by weight; use analytical pure phosphoric acid Sodium dihydrogen, disodium hydrogen phosphate reagent and deionized water prepare 0.5 molar concentration of sodium dihydrogen phosphate and disodium hydrogen phosphate equimolar concentration buffer solution as solidified liquid; The composite bone cement slurry was prepared with a solid-liquid ratio of 0.6:1. The prepared bone cement slurry can be directly injected into the bone defect with a syringe for use. The above-prepared bone cement slurry is injected into a mold to solidify for 1.5 hours, and then dried at 80-100° C. to prepare a bulk filling material for filling and treating open bone defects.

Animal experiments confirmed that, compared with the calcium silicate bulk filling material without Mg ₆₄ Zn ₃₀ Ca ₁ Sr ₅ amorphous fibers, the degradation speed of the bulk filling material after compounding was accelerated, holes appeared on the surface, and the repair speed of cortical bone was significantly accelerated.

Matters not addressed in the present invention are known in the art.

The above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and the purpose thereof is to enable those who are familiar with the art to understand the content of the present invention and implement them accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.

Claims (9)

1. A magnesium-based amorphous-calcium phosphate/calcium silicate composite filler with high bioactivity is characterized in that: the injectable calcium phosphate/calcium silicate filler is added with magnesium-based amorphous powder/fiber to form a composite filler.

2. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous alloy comprises MgZnCaSr, wherein the Zn content is as follows: 21-40 at.%, the Ca content is: 2-7 at.%, Sr content: 0-5 at.%, balance Mg.

3. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous powder/fiber content accounts for 1-30 wt% of the composite filler.

4. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous powder is spherical or irregular, and the particle size is less than 1 mm.

5. The magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, wherein: the magnesium-based amorphous fiber has the length of 1-30mm and the width of 0.1-1 mm.

6. A method for preparing the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 1, comprising the steps of:

(1) mixing the calcium phosphate/calcium silicate bone cement solid-phase powder with the magnesium-based amorphous powder/fiber to obtain solid-phase composite powder;

(2) preparing a buffer solution with the equal molar concentration of 0.2-1.0 mol% of sodium dihydrogen phosphate and disodium hydrogen phosphate by using analytically pure or analytically pure sodium dihydrogen phosphate, a disodium hydrogen phosphate reagent and deionized water or distilled water as a curing solution;

(3) and (3) preparing the solid-phase composite powder prepared in the step (1) and the curing liquid prepared in the step (2) according to the solid-liquid ratio of 0.1-3: 1 to prepare the composite bone cement slurry.

7. The method for preparing the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler according to claim 6, wherein: and (4) injecting the bone cement slurry prepared in the step (3) into a mold, curing for 20 minutes to 6 hours, and then drying at 80 to 100 ℃ to prepare the blocky filling material.

8. Use of a magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method of claim 6 for the preparation of injectable products for bone tissue wound repair.

9. Use of the magnesium-based amorphous-calcium phosphate/calcium silicate composite filler prepared by the method of claim 7 for preparing a filler for open bone defects.

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