Mgznca / snzn metallic glass composite and method of making same

Abstract

The application provides a MgZnCa / SnZn metal glass composite material and a preparation method thereof, and the preparation method comprises the following steps: step S1, preparing MgZnCa metal glass powder and SnZn powder; step S2, uniformly mixing the MgZnCa metal glass powder and the SnZn powder, and performing discharge plasma sintering on the obtained mixture to obtain the MgZnCa / SnZn metal glass composite material; wherein the mass ratio of the SnZn in the mixture is 40%-80%. The MgZnCa / SnZn bulk metal glass composite material obtained by the technical scheme has excellent mechanical properties, the compressive strength is more than 110MPa, and the elongation rate is more than 15%, and the processing requirements of a biomedically implantable material are reached; and the MgZnCa / SnZn bulk metal glass composite material is nontoxic, degradable, and has better corrosion resistance performance than the MgZnCa bulk metal glass alloy in both instantaneous and long-term performances.

Description

Technical Field

[0001] This invention belongs to the field of metallic glass composite materials technology, and particularly relates to a MgZnCa / SnZn metallic glass composite material and its preparation method. Background Technology

[0002] With the maturation of metallic glass preparation technology and the development of various systems, research on metallic glasses and their properties has become increasingly in-depth. Various Mg-based metallic glasses with different compositions have been gradually developed. Due to their disordered microstructure, unlike crystalline alloys, Mg-based metallic glasses exhibit significantly higher fracture strength than crystalline magnesium and magnesium alloys. Furthermore, compared to crystalline magnesium alloys, the boundary-free glassy matrix effectively delays the growth of corrosion pits, demonstrating excellent corrosion resistance. Therefore, the superior comprehensive properties of Mg-based metallic glasses show great potential for development in the field of biodegradable medical applications.

[0003] For medical metallic materials, ensuring the safety of implants and avoiding adverse effects from ion release is paramount. Therefore, non-toxic metallic elements beneficial to human tissues should be selected. The MgZnCa metallic glass system, composed of Mg, Zn, and Ca—three trace elements essential to the human body—ensures biocompatibility and is currently the most widely accepted metallic glass alloy system in biodegradable biomedical materials. Numerous experimental results in in vitro cell experiments and in vivo animal implantation studies have demonstrated its excellent biocompatibility, rapidly making it a research hotspot in the field of biodegradable medical materials. However, compared to crystalline alloys, the biggest disadvantage of metallic glasses lies in their narrow shear bands, leading to brittle fracture. The Mg-Zn-Ca metallic glass system, in particular, is highly brittle, forming numerous fragments upon fracture. This characteristic hinders subsequent processing and in vivo implantation, significantly limiting its application prospects. Despite extensive research, no breakthrough has been achieved. Therefore, how to effectively improve the brittleness of Mg-Zn-Ca bulk metallic glasses is currently the most pressing problem that needs to be solved.

[0004] Currently reported Mg-Zn-Ca metallic glasses have virtually no plasticity. Some researchers have improved Mg-Zn-Ca metallic glasses by introducing rare earth elements (such as Y and La) into the metallic glass matrix (elongation of about 3%). However, the biocompatibility of rare earth elements is currently highly controversial, so introducing rare earth elements into implants should not be the primary choice. Summary of the Invention

[0005] To address the above technical problems, this invention discloses a MgZnCa / SnZn metallic glass composite material and its preparation method, which has excellent mechanical properties, is non-toxic, and biodegradable, and can be used as a material for biomedical implant scaffolds.

[0006] The technical solution adopted by this invention is as follows:

[0007] A biodegradable MgZnCa metallic glass composite material and its preparation method, comprising the following steps:

[0008] Step S1: Prepare MgZnCa metallic glass powder and SnZn powder;

[0009] Step S2: Mix MgZnCa metallic glass powder and SnZn powder evenly, and perform spark plasma sintering on the resulting mixture to obtain MgZnCa / SnZn metallic glass composite material; wherein, the mass ratio of SnZn in the mixture is 40%-80%.

[0010] As a further improvement of the present invention, the mass ratio of Sn to Zn in the mixture is 50% to 70%.

[0011] As a further improvement of the present invention, the mass ratio of Sn to Zn in the mixture is 70%.

[0012] As a further improvement of the present invention, the MgZnCa metallic glass powder has an atomic ratio of Mg 66 Zn 30 Ca4 metallic glass powder, the SnZn powder having an atomic ratio of Sn 85 Zn 15 powder.

[0013] As a further improvement of the present invention, the MgZnCa metallic glass powder is prepared using existing techniques, and can be prepared by the following steps:

[0014] According to Mg 66 Zn 30 Ca4 raw materials, including Mg, Zn, and Ca, were weighed according to the nominal proportions and prepared into a master alloy ingot using a vacuum induction melting method. The prepared alloy ingot was then remelted and spherical Mg alloys were prepared using an argon atomization process. 66 Zn 30 Ca4 granular powder, Mg 66 Zn 30 Ca4 particles were ball-milled to obtain MgZnCa metallic glass powder.

[0015] As a further improvement of the present invention, the effective ball milling time is 6-10 hours, the rotation speed is 200-300 rpm, and the ball-to-material ratio is 15-25:1. More preferably, the effective ball milling time is 8 hours, the rotation speed is 250 rpm, and the ball-to-material ratio is 20:1.

[0016] As a further improvement of the present invention, the SnZn powder is prepared using existing techniques, and can be prepared by the following steps:

[0017] According to Sn 85 Zn 15 Sn and Zn raw materials were weighed in the nominal proportion and prepared into master alloy ingots using vacuum induction melting. The prepared master alloy ingots were then prepared into spherical granular powders using vacuum atomization.

[0018] As a further improvement of the present invention, when using the vacuum induction melting method, the alloy melting temperature is about 473K and the injection pressure is set to 3MPa.

[0019] As a further improvement of the present invention, the spark plasma sintering is carried out under vacuum conditions and adopts a three-stage sintering process. The first stage has a heating rate of 11-12 K / min, a pressure increase rate of 82-88 MPa / min, and a time of 6-10 min; the second stage has a heating rate of 2-3 K / min, with the pressure kept constant, and a time of 6-10 min; the third stage has a heating rate of 1.5-2.5 K / min, with the pressure kept constant, and a time of 5-8 min; when the temperature reaches 383 K, the pressure is kept constant and the temperature is held for 3-8 min; after the sintering process is completed, the sample is cooled to room temperature with the furnace.

[0020] Furthermore, the first stage heating rate was 11.5 K / min, the pressure increase rate was 86 MPa / min, and the time was 7 min; the second stage heating rate was 2.5 K / min, the pressure was kept constant, and the time was 8 min; the third stage heating rate was 1.7 K / min, the pressure was kept constant, and the time was 6 min; when the temperature reached 383 K, the pressure was kept constant and the temperature was held for 5 min; after the sintering process was completed, the sample was cooled to room temperature with the furnace.

[0021] This invention discloses a MgZnCa / SnZn metallic glass composite material, which is prepared by the preparation method of MgZnCa / SnZn metallic glass composite material as described in any one of the above claims.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] The MgZnCa / SnZn bulk metallic glass composite material obtained by adding SnZn and sintering with discharge plasma using the technical solution of this invention exhibits excellent mechanical properties, with a compressive strength exceeding 110 MPa and significant plastic strain, and an elongation exceeding 15%. Its mechanical properties fully meet the processing requirements for biomedical implantable materials. The corrosion resistance of this composite material is superior to that of MgZnCa bulk metallic glass alloy in both instantaneous and long-term applications. This composite material is biodegradable, with a complete degradation time approximately 2-4 times that of MgZnCa bulk metallic glass. After immersion in simulated corrosive solutions, its mechanical properties decrease by only about 20%, while maintaining good plasticity.

[0024] Furthermore, the composite material has a more complete skeleton, exhibiting stronger resistance to hydrogen pressure, and its degradation rate can be controlled by adjusting the proportion of SnZn alloy in the composite material. In particular, the composite material with a SnZn mass ratio of 70% exhibits an ultimate compressive strength of 110 MPa, compressive plasticity exceeding 25%, and does not fracture after testing, meeting processing requirements. Its Young's modulus is 52 GPa, close to that of human bone, and its complete degradation time is approximately four times that of MgZnCa metallic glass, achieving a combination of excellent mechanical properties and corrosion resistance. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the sintering process of discharge plasma sintering according to an embodiment of the present invention.

[0026] Figure 2 These are the X-ray diffraction patterns of the metallic glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention.

[0027] Figure 3 These are SEM images of metal-glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention. (a) to (d) are SEM images of metal-glass composite materials with SnZn mass percentages of 10%, 20%, 30%, and 40%, respectively, and (e1) and (e2) are SEM images of metal-glass composite materials with SnZn mass percentages of 50% at different magnifications.

[0028] Figure 4 These are SEM images of metal-glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention. (a1) and (a2) are SEM images of the metal-glass composite material with 60% SnZn mass percentage at different magnifications, respectively; (b1) and (b2) are SEM images of the metal-glass composite material with 70% SnZn mass percentage at different magnifications, respectively; (c) is the SEM image of the metal-glass composite material with 80% SnZn mass percentage; and (d) is the SEM image of the metal-glass composite material with 90% SnZn mass percentage.

[0029] Figure 5 These are electron backscatter diffraction images of metal-glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention, wherein the SnZn mass percentages in (a) to (c) are 50%, 60%, and 70%, respectively.

[0030] Figure 6 These are EDS energy dispersive spectroscopy images of metallic glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention. Among them, (a1) and (a2) are EDS images of metallic glass composite materials with a SnZn mass percentage of 40%, and (b1) and (b2) are EDS images of metallic glass composite materials with a SnZn mass percentage of 70%.

[0031] Figure 7 These are fracture morphology diagrams of metal-glass composite materials obtained by sintering with different SnZn mass percentages according to embodiments of the present invention, wherein the SnZn mass percentages in (a) to (d) are 10%, 20%, 30%, and 40%, respectively.

[0032] Figure 8 These are morphology images of different locations on the fracture cross-section of a composite material with a SnZn alloy ratio of 50% according to an embodiment of the present invention, wherein (a) and (b) are morphology images of different locations, respectively.

[0033] Figure 9 This is a Young's modulus distribution diagram of the metal-glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention.

[0034] Figure 10 These are mechanical property diagrams of metal-glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention, where (a) represents hardness and (b) represents stress-strain curves.

[0035] Figure 11 These are electrical performance diagrams of metal-glass composite materials obtained after sintering with different SnZn mass percentages according to embodiments of the present invention, where (a) is the open-circuit voltage and (b) is the dynamic polarization curve.

[0036] Figure 12 This is a comparison of the results of immersing the metal glass composite material obtained by sintering 70% SnZn by mass in Hank's solution for 20 days with the results of immersing MgZnCa metal glass material in Hank's solution for 7 days. (a) is the corrosion rate, (b) is the macroscopic morphology of MgZnCa metal glass after immersion for 7 days, and (c) is the macroscopic morphology of the metal glass composite material obtained by sintering 70% SnZn by mass after immersion for 7 days.

[0037] Figure 13The compression curves of the metal-glass composite materials obtained by sintering different SnZn mass percentages in embodiments of the present invention after immersion in Hank's solution for 5 days are shown.

[0038] Figure 14 The mechanical properties of the metal-glass composite materials obtained by sintering different SnZn mass percentages in the embodiments of the present invention after immersion in Hank's solution for 5 days are shown, where (a) is the ultimate compressive strength and (b) is the change in Young's modulus.

[0039] Figure 15 The pH value of the metal-glass composite material obtained by sintering different mass percentages of SnZn in the embodiments of the present invention is obtained by immersing it in Hank's solution for different numbers of days.

[0040] Figure 16 The images show the surface morphology of the metal-glass composite materials obtained by sintering with different SnZn mass percentages in the embodiments of the present invention after being immersed in Hank's solution for one day; wherein the SnZn mass percentages in (a) to (c) are 50%, 60%, and 70%, respectively.

[0041] Figure 17 The images show the surface morphology of the metal-glass composite material obtained by sintering 70% SnZn by mass in Hank's solution after different days of immersion. (a) to (c) show the surface morphology after 1 day, 3 days, and 5 days, respectively. (d1) and (d2) show the surface morphology after 7 days of immersion at different magnifications. (e) shows the surface morphology after 9 days of immersion.

[0042] Figure 18 The variation in the corrosion layer thickness of the metallic glass composite material obtained after sintering 70% by mass of SnZn in the embodiment of the present invention; where (a) to (c) are 1 day, 5 days, and 9 days, respectively.

[0043] Figure 19 This is the X-ray diffraction pattern of the metallic glass composite material obtained by sintering 70% SnZn by mass in an embodiment of the present invention after immersion in Hank's solution.

[0044] Figure 20 This is the surface elemental energy spectrum of the metal-glass composite material obtained by sintering 60% SnZn by mass in an embodiment of the present invention after immersion in Hank's solution for 1 day.

[0045] Figure 21 This is the surface elemental energy spectrum of the metal-glass composite material obtained by sintering 60% SnZn by mass in an embodiment of the present invention after immersion in Hank's solution for 7 days. Detailed Implementation

[0046] The preferred embodiments of the present invention will be described in further detail below.

[0047] Example 1

[0048] A MgZnCa / SnZn metallic glass composite material, the preparation method of which includes the following steps:

[0049] Mg 66 Zn 30 Ca4 (atomic percentage, hereinafter referred to as MgZnCa) was prepared into a master alloy ingot using vacuum induction melting technology according to the nominal proportion. The prepared alloy ingot was then remelted and spherical Mg was prepared using an argon atomization process. 66 Zn 30 Ca4 granular powder.

[0050] Sn 85 Zn 15 (Atomic percentage, hereinafter referred to as SnZn) According to the nominal ratio, a master alloy ingot was prepared by vacuum induction melting. The prepared alloy was then prepared into spherical powder particles by vacuum atomization. The alloy melting temperature was about 473K and the injection pressure was set to 3MPa.

[0051] Ball milling pretreatment was performed on MgZnCa metallic glass powder (effective ball milling time 8h, speed 250rpm, ball-to-material ratio 20:1) to change the morphology of the powder spheres.

[0052] The ball-milled MgZnCa and SnZn powders were mixed according to a set mass ratio. In this embodiment, the proportion of SnZn powder was varied, and experiments were conducted with the mass ratio of MgZnCa to SnZn powder as 0:10, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2, 9:1, and 10:0. The mixing method was mechanical mixing, and the time was 36 hours.

[0053] The uniformly mixed composite material powder is solidified and sintered using spark plasma sintering technology. The sintering process is as follows: Figure 1 As shown, specifically: under vacuum conditions, a three-stage sintering process was adopted. The first stage had a heating rate of 11.5 K / min, a pressure increase rate of 86 MPa / min, and a time of 7 min; the second stage had a heating rate of 2.5 K / min, with the pressure kept constant, and a time of 8 min; the third stage had a heating rate of 1.7 K / min, with the pressure kept constant, and a time of 6 min; when the temperature reached 383 K, the pressure was kept constant, and the temperature was held for 5 min; after the sintering process was completed, the sample was cooled to room temperature with the furnace and then removed.

[0054] This embodiment yielded bulk metallic glass composite material samples of MgZnCa / SnZn with MgZnCa, SnZn, and SnZn mass percentages of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%, respectively. The obtained samples were tested for microstructure, mechanical properties, and corrosion resistance.

[0055] The X-ray diffraction pattern of the composite material after sintering is shown in the figure. Figure 2 As shown in the figure. SEM images of the metal-glass composites obtained after sintering with different SnZn mass percentages are shown in the figure. Figure 3 and Figure 4 As shown, the electron backscatter diffraction image is as follows: Figure 5 As shown, the EDS energy dispersive spectroscopy (EDS) image is as follows: Figure 6 As shown, the morphology images at different locations on the fracture cross-section of the composite material are as follows: Figure 7 and Figure 8 As shown.

[0056] Regarding mechanical properties, the densities of composite materials with different SnZn mass percentages are shown in Table 1, and the Young's modulus distribution diagram is shown in... Figure 9 As shown in Table 2, the ultimate compressive strength and hardness of composite materials with different SnZn mass percentages are shown in Table 3. The hardness and stress-strain curves are shown in Table 4. Figure 10 As shown.

[0057] Table 1 Density of composite materials with different alloy ratios

[0058]

[0059] Table 2 Ultimate compressive strength and hardness of composite material blocks

[0060]

[0061] It is evident that metallic glass composites with a SnZn mass percentage exceeding 50% begin to exhibit macroscopic plastic deformation under external load. Composites with SnZn mass percentages of 50%, 60%, and 70% exhibit compressive strengths exceeding 110 MPa and elongations exceeding 15%, all meeting the processing requirements for biomedical implantable materials.

[0062] The open-circuit voltage and dynamic polarization curves of composite materials with different SnZn mass percentages are shown in the figure. Figure 11As shown in Table 3, the fitting parameters for the Tafel curve are as follows. It can be seen that the corrosion potential of the MgZnCa / SnZn metallic glass composite material shifts positively compared to the MgZnCa alloy, indicating that the instantaneous corrosion resistance of the MgZnCa / SnZn composite material is superior to that of the MgZnCa metallic glass. This further demonstrates that the addition of SnZn increases the open-circuit potential and self-corrosion potential of the MgZnCa metallic glass composite material, thereby improving its corrosion resistance.

[0063] Table 3. Tafel curve fitting parameters

[0064]

[0065] The corrosion rates of MgZnCa after immersion in Hank's solution for 7 days, and of a metallic glass composite with 70% SnZn by mass after immersion in Hank's solution for 20 days, are as follows: Figure 12 As shown in (a), the macroscopic morphology of both after 7 days of soaking is as follows. Figure 12 (b) and Figure 12 As shown in (c), the addition of SnZn alloy significantly reduces the corrosion rate of MgZnCa. The long-term degradation rate of the MgZnCa / SnZn composite material is much lower than that of the MgZnCa metallic glass. The MgZnCa metallic glass fragments after immersion for 7 days, while the MgZnCa / SnZn metallic glass composite material maintains its surface integrity after immersion for 20 days. This also demonstrates that the degradation rate of the composite material can be controlled by adjusting the ratio of the two phases.

[0066] Compression curves of metallic glass composites with SnZn mass percentages of 50%, 60%, and 70% after immersion in Hank's solution for 5 days are shown below. Figure 13 As shown, the ultimate compressive strength is as follows Figure 14 As shown in (a), the change in Young's modulus is as follows: Figure 14 As shown in (b); the pH values ​​of Hank's solution after soaking for different numbers of days are as follows. Figure 15 As shown; the surface morphology after soaking for one day is as follows. Figure 16 As shown. The surface morphology of the metal-glass composite material obtained after sintering 70% SnZn by mass for different days is shown. Figure 17 As shown, the change in corrosion layer thickness after immersion for different days is as follows: Figure 18 As shown, the X-ray diffraction patterns of the materials after immersion for different days are as follows: Figure 19 As shown. Example: The surface elemental energy spectrum of a metallic glass composite material obtained by sintering 60% by mass Sn and Zn, after immersion in Hank's solution for one day is shown below. Figure 20 As shown, the elemental energy spectrum of the surface after soaking for 7 days is as follows: Figure 21 As shown.

[0067] The performance comparison above shows that as the SnZn ratio increases, the SnZn grain size gradually increases, the composite material gradually exhibits plastic deformation, the strength gradually decreases, and the corrosion resistance gradually increases. Therefore, the expansion of shear bands can be hindered and the number of shear bands increased by changing the ratio of the MgZnCa / SnZn metallic glass composite material, while simultaneously adjusting the SnZn grain size.

[0068] The corrosion resistance of the composite material is superior to that of MgZnCa bulk metallic glass alloy in both instantaneous and long-term conditions. The time for complete degradation is about 2-4 times that of MgZnCa bulk metallic glass. After immersion in simulated corrosive solution, the mechanical properties only decrease by about 20%, while maintaining good plasticity.

[0069] In particular, the SnZn composite material with a mass percentage of 70% has an ultimate compressive strength of 110 MPa, a compressive plasticity of over 25%, does not fracture after testing, has a Young's modulus of 52 GPa, which is close to that of human bone, and a complete degradation time of about 4 times that of MgZnCa metallic glass, demonstrating a combination of excellent mechanical properties and corrosion resistance.

[0070] With the increase of the SnZn alloy ratio, the composite material has a more complete skeleton and stronger resistance to the pressure generated by hydrogen. Furthermore, the degradation rate can be controlled by adjusting the SnZn alloy ratio in the composite material.

[0071] The above description, in conjunction with specific preferred embodiments, provides a further detailed explanation of the present invention. It should not be construed that the specific implementation of the present invention is limited to these descriptions. For those skilled in the art, various simple deductions or substitutions can be made without departing from the concept of the present invention, and all such modifications and substitutions should be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a MgZnCa / SnZn metallic glass composite material, characterized in that: Includes the following steps: Step S1: Prepare MgZnCa metallic glass powder and SnZn powder; Step S2: Mix MgZnCa metallic glass powder and SnZn powder evenly, and perform spark plasma sintering on the resulting mixture to obtain MgZnCa / SnZn metallic glass composite material; wherein, the mass ratio of SnZn in the mixture is 40%-80%; The spark plasma sintering is carried out under vacuum conditions and employs a three-stage sintering process. The first stage has a heating rate of 11-12 K / min, a pressure increase rate of 82-88 MPa / min, and a time of 6-10 min. The second stage has a heating rate of 2-3 K / min, with the pressure kept constant, and a time of 6-10 min. The third stage has a heating rate of 1.5-2.5 K / min, with the pressure kept constant, and a time of 5-8 min. When the temperature reaches 383 K, the pressure is kept constant, and the temperature is held for 3-8 min. After the sintering process is completed, the sample is cooled to room temperature with the furnace.

2. The method for preparing the MgZnCa / SnZn metallic glass composite material according to claim 1, characterized in that: The mass ratio of Sn to Zn in the mixture is 50% to 70%.

3. The method for preparing the MgZnCa / SnZn metallic glass composite material according to claim 2, characterized in that: The mass ratio of Sn to Zn in the mixture is 70%.

4. The method for preparing the MgZnCa / SnZn metallic glass composite material according to claim 2, characterized in that: The MgZnCa metallic glass powder is Mg 66 Zn 30 Ca4 metallic glass powder, the SnZn powder is Sn 85 Zn 15 powder.

5. The method for preparing the MgZnCa / SnZn metallic glass composite material according to claim 4, characterized in that: The MgZnCa metallic glass powder was prepared using the following steps: According to Mg 66 Zn 30 Ca4 raw materials, including Mg, Zn, and Ca, were weighed according to the nominal proportions and prepared into a master alloy ingot using a vacuum induction melting method. The prepared alloy ingot was then remelted and spherical Mg alloys were prepared using an argon atomization process. 66 Zn 30 Ca4 granular powder, Mg 66 Zn 30 Ca4 particles were ball-milled to obtain MgZnCa metallic glass powder.

6. The method for preparing the MgZnCa / SnZn metallic glass composite material according to claim 5, characterized in that: The effective ball milling time is 6-10 hours, the rotation speed is 200-300 rpm, and the ball-to-material ratio is 15-25:

1.

7. The method for preparing the MgZnCa / SnZn metallic glass composite material according to claim 4, characterized in that: The SnZn powder was prepared using the following steps: According to Sn 85 Zn 15 Sn and Zn raw materials were weighed in the nominal proportion and prepared into master alloy ingots using vacuum induction melting. The prepared master alloy ingots were then prepared into spherical granular powders using vacuum atomization.

8. A MgZnCa / SnZn metallic glass composite material, characterized in that: It is prepared using the method for preparing MgZnCa / SnZn metallic glass composite material as described in any one of claims 1 to 7.

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