Medical degradable magnesium-based composite alloy material as well as preparation method and application thereof

Abstract

The invention provides a medical degradable magnesium-based composite alloy material as well as a preparation method and application thereof, and belongs to the technical field of biological materials. The magnesium-based composite alloy material is formed by compounding multiple binary alloys such as Mg-Cu, Mg-Ca, Mg-Sr and Mg-Zn, multiple binary magnesium alloy powder is polymerized through high-temperature large deformation to prepare the composite magnesium alloy material, synergistic release of multiple alloy elements can be achieved, the biological function provided by the alloy elements is achieved, and meanwhile, the composite magnesium alloy material has the advantages of being simple in preparation process, low in cost and good in application prospect. And the generation of a second phase in the material can be reduced or even avoided, so that the composite alloy material has good degradation performance. The material has the biggest advantage that the material not only can realize diversified release of metal ions in the degradation process, but also can maintain relatively stable degradation performance.

Description

Technical Field

[0001] The present invention relates to the technical field of biomaterials, and in particular to a medical degradable magnesium-based composite alloy material and a preparation method and application thereof. Background Art

[0002] As implantable devices in the body, medical magnesium metal materials can be completely degraded after service, and the degradation products are absorbed by the human body without any toxic side effects, avoiding the need for secondary surgery to remove the device. By adding trace elements with physiological effects to magnesium, functional ions are released during the degradation process, which can give the material certain biological functions, such as the antibacterial effect of copper ions, the anti-inflammatory effect of zinc ions, and the bone-promoting effect of strontium ions.

[0003] If the coordinated release of multiple functional ions and multiple biological functions are to be achieved in magnesium, it is necessary to add multiple alloying elements to magnesium, that is, to design and prepare multi-element magnesium alloys by means of alloying. However, it is difficult to avoid the generation of second phases in magnesium alloys with more than ternary elements. During clinical use, multi-element magnesium alloys will rapidly corrode and degrade due to the galvanic corrosion behavior between the second phase and the matrix during the degradation process, which is difficult to meet actual needs. Therefore, there is currently a lack of a design concept for magnesium materials that can achieve diversified release of ions while maintaining relatively stable degradation performance. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a medical degradable magnesium-based composite alloy material and a preparation method and application thereof. The preparation method provided by the present invention is simple to operate, and the obtained medical degradable magnesium-based composite alloy material can not only realize the diversified release of metal ions during the degradation process, but also maintain relatively stable degradation performance.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing a medical degradable magnesium-based composite alloy material, comprising the following steps:

[0007] The metal powders are mixed and plastic processed under heating conditions to obtain a medical degradable magnesium-based composite alloy material;

[0008] The metal powder includes a plurality of binary magnesium alloy powders, or includes a plurality of binary alloy powders and high-purity magnesium powder;

[0009] The binary magnesium alloy powder is selected from two or more of Mg-Cu alloy, Mg-Ca alloy, Mg-Sr alloy, Mg-Zn alloy and Mg-Mn alloy;

[0010] The plastic processing is one or more of extrusion, rolling and forging.

[0011] Preferably, the mass content of the functional element in the binary magnesium alloy is 0-5%, and is not 0.

[0012] Preferably, the particle size of the binary magnesium alloy powder is 1 μm to 1 mm.

[0013] Preferably, the heating condition has a temperature of 150-500°C.

[0014] Preferably, the extrusion ratio of the extrusion is 5 to 20:1.

[0015] Preferably, the rolling is performed in n passes, where n≥1; the deformation amount of the first pass of the rolling is ≥30%, and the deformation amount of each subsequent pass is 10-20%.

[0016] Preferably, the forging temperature is 150-450° C., the forging pass is ≥1, and the deformation amount of a single pass is ≥10%.

[0017] Preferably, before the plastic processing, the mixed metal powder is also cold pressed;

[0018] The cold pressing is performed at a pressure of 25-26 MPa and for a time of 3 hours.

[0019] The invention provides a medical degradable magnesium-based composite alloy material prepared by the above preparation method.

[0020] The present invention provides application of the above-mentioned medical degradable magnesium-based composite alloy material in preparing medical implant materials.

[0021] The present invention provides a preparation method of a medical degradable magnesium-based composite alloy material, comprising the following steps: mixing metal powders, performing plastic processing under heating conditions, and obtaining a medical degradable magnesium-based composite alloy material; the metal powders include a variety of binary magnesium alloy powders, or include a variety of binary alloy powders and high-purity magnesium powders; the binary magnesium alloy powders are selected from two or more of Mg-Cu alloy, Mg-Ca alloy, Mg-Sr alloy, Mg-Zn alloy and Mg-Mn alloy; the plastic processing is one or more of extrusion, rolling and forging. The magnesium-based composite alloy material of the present invention is mainly composed of a variety of binary alloys such as Mg-Cu, Mg-Ca, Mg-Sr, Mg-Zn, etc., and a variety of binary magnesium alloy powders are polymerized to prepare a composite magnesium alloy material through high-temperature large deformation, which can realize the synergistic release of its various alloy elements, while completing the biological functions provided by the alloy elements, and can reduce or even avoid the generation of the second phase in the material, so that the composite alloy material has good degradation performance. Its greatest advantage is that the material can not only realize the diversified release of metal ions during the degradation process, but also maintain relatively stable degradation performance.

[0022] Furthermore, the magnesium-based composite alloy prepared by the present invention adopts a high-temperature large-deformation welding process. After plastic processing and compounding, the alloy has a fine-grained structure and thus has good comprehensive mechanical properties, solving the problem of low strength of magnesium alloys in medical applications.

[0023] Furthermore, during the multi-pass plastic deformation process of the present invention, the alloy always has good plasticity and fluidity, and no cracking occurs, which promotes further uniform refinement of its grains. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 The metallographic morphology of the medical degradable magnesium-based composite alloy material obtained in Examples 1 to 3 and the multi-element alloy material obtained in Comparative Example 3;

[0025] Figure 2 The tensile test stress-strain curves of the medical degradable magnesium-based composite alloy materials obtained in Examples 1 to 3 and the multi-element alloy material obtained in Comparative Example 3;

[0026] Figure 3 The tensile test stress-strain curves of the medical degradable magnesium-based composite alloy material obtained in Example 2 and the alloy materials of Comparative Examples 1 to 3 are shown. DETAILED DESCRIPTION

[0027] The present invention provides a method for preparing a medical degradable magnesium-based composite alloy material, comprising the following steps:

[0028] The metal powders are mixed and plastic processed under heating conditions to obtain a medical degradable magnesium-based composite alloy material;

[0029] The metal powder includes a plurality of binary magnesium alloy powders, or includes a plurality of binary alloy powders and high-purity magnesium powder;

[0030] The binary magnesium alloy powder is selected from two or more of Mg-Cu alloy, Mg-Ca alloy, Mg-Sr alloy, Mg-Zn alloy and Mg-Mn alloy;

[0031] The plastic processing is one or more of extrusion, rolling and forging.

[0032] The present invention mixes metal powders and performs plastic processing under heating conditions to obtain a medical degradable magnesium-based composite alloy material. In the present invention, the metal powders include multiple binary magnesium alloy powders, or multiple binary alloy powders and high-purity magnesium powders.

[0033] In the present invention, the plurality of binary magnesium alloy powders are preferably selected from two or more of Mg-Cu alloy, Mg-Ca alloy, Mg-Sr alloy, Mg-Zn alloy and Mg-Mn alloy. In the present invention, the mass content of the functional elements (i.e., Cu, Ca, Sr, Zn or Mn) in the Mg-Cu alloy, Mg-Ca alloy, Mg-Sr alloy, Mg-Zn alloy and Mg-Mn alloy is preferably 0-5% and not 0, specifically 0.2%, 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5%. In the present invention, the purity of the high-purity magnesium powder is preferably ≥99.8%.

[0034] In the present invention, the binary magnesium alloy powder is preferably obtained by grinding an ingot. In the present invention, the particle size of the binary magnesium alloy powder is preferably 1 μm to 1 mm, more preferably 10 to 500 μm.

[0035] In the present invention, when the metal powder includes multiple binary magnesium alloy powders, the present invention has no special requirements on the amount of each binary magnesium alloy powder, and can be designed accordingly according to the functional requirements of the medical degradable magnesium-based composite alloy material.

[0036] In the present invention, when the metal powder includes a plurality of binary alloy powders and high-purity magnesium powder, the present invention has no special requirements on the mass content of the high-purity magnesium powder in the metal powder; the present invention has no special requirements on the amount of each binary magnesium alloy powder in the plurality of binary alloy powders, and the corresponding design can be made according to the functional requirements of the medical degradable magnesium-based composite alloy material.

[0037] In the present invention, the heating temperature is preferably 150-500°C, more preferably 300-400°C; as a specific embodiment of the present invention, the heating temperature is 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C or 500°C.

[0038] In the present invention, before the plastic working, the mixed metal powder is preferably cold pressed. In the present invention, the pressure of the cold pressing is preferably 25-26 MPa, and the time is preferably 3 hours. In the present invention, before the cold pressing, the mixed powder is preferably vacuum pressed.

[0039] In the present invention, the plastic working is one or more of extrusion, rolling and forging. In the present invention, when the plastic working is extrusion, the extrusion ratio of the extrusion is preferably 5 to 20:1, more preferably 10:1.

[0040] In the present invention, when the plastic working is rolling, the rolling is preferably n-pass rolling, where n is a positive integer ≥1. As a specific embodiment of the present invention, n is 1, 2, 3, 4 or 5. In the present invention, the deformation amount of the first pass of the rolling is preferably ≥30%, and the deformation amount of each subsequent pass is preferably 10-20%.

[0041] In the present invention, when the plastic working is forging, the forging is preferably hammer forging; in the present invention, the forging temperature is preferably 150-450° C., specifically 150° C., 200° C., 250° C., 300° C., 350° C., 400° C. or 450° C. In the present invention, the forging pass is preferably ≥1, and the deformation amount of a single pass is preferably ≥10%.

[0042] The invention provides a medical degradable magnesium-based composite alloy material prepared by the above preparation method.

[0043] The present invention provides the use of the above-mentioned medical degradable magnesium-based composite alloy material in the preparation of medical implant materials. In the present invention, the medical implant material is preferably a bone repair material.

[0044] The medical degradable magnesium-based composite alloy material provided by the present invention and its preparation method and application are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0045] Example 1 3-pass rolling

[0046] Mg-0.1Cu, Mg-0.1Ca, Mg-1.5Sr and Mg-1.25Zn alloy powders were used as raw materials, mixed in a mass ratio of 1:1:1:1, vacuum-pressed, and cold-pressed for 3 hours at a maximum pre-pressing pressure of 26 MPa to obtain a pre-pressed alloy.

[0047] A pre-pressed alloy with a size of 40.6*30.5 mm was used as a sample, and the pre-pressed alloy was subjected to three passes of rolling. The first pass was rolled at 400°C, and the deformation of the pass was 50%. The second and third passes were all rolled along the RD direction. After three passes of rolling, the total deformation was 90%, and a medical degradable magnesium-based composite alloy material was obtained, which was recorded as MCH-3.

[0048] Example 2 4-pass rolling

[0049] Mg-0.2Cu, Mg-0.2Ca, Mg-0.5Sr and Mg-2Zn alloy powders were used as raw materials, mixed in a mass ratio of 1:1:1:4, vacuum-pressed, and cold-pressed for 3 hours at a maximum pre-pressing pressure of 26 MPa to obtain a pre-pressed alloy.

[0050] A pre-pressed alloy with a size of 40.6*30.5 mm was used as a sample, and the pre-pressed alloy was subjected to 4 passes of rolling. The first pass was rolled at 400°C, and the first to fourth passes were all rolled in a 45° direction. The deformation amount in the first pass was 58%, and the total deformation amount after 4 passes of rolling was 95%, and a medical degradable magnesium-based composite alloy material was obtained, which was recorded as MCH-4.

[0051] Example 3 5-pass rolling

[0052] High-purity magnesium, Mg-0.1Cu, Mg-0.1Ca, Mg-0.5Sr, and Mg-2Zn metal powders are used as raw materials, mixed in a mass ratio of 2:1:1:1:5, and after vacuum pressing, cold pressing is performed at a maximum pre-pressing pressure of 26 MPa for 3 hours to obtain a pre-pressed alloy.

[0053] A pre-pressed alloy with a size of 40.6*30.5 mm was used as a sample, and the pre-pressed alloy was subjected to 5 passes of rolling. The first pass was rolled at 400°C, and the second, third, fourth, and fifth passes were rolled perpendicular to the first pass. The deformation amount of the first pass was 58%, and the total deformation amount after 5 passes of rolling was 97.5%, and a medical degradable magnesium-based composite alloy material was obtained, which was recorded as MCH-5.

[0054] Comparative Example 1

[0055] The cast Mg-0.1wt% Cu alloy was used as comparative example 1, and was recorded as Mg-0.1Cu.

[0056] Comparative Example 2

[0057] The cast Mg-0.2wt%.Ca alloy was used as comparative example 2, and was recorded as Mg-0.2Ca.

[0058] Comparative Example 3

[0059] The cast Mg-0.1wt%.Ca-0.1wt%.Cu-0.5wt%.Sr-1.25wt%.Zn multi-element alloy was subjected to one extrusion deformation with a deformation amount of 90% and an initial die temperature of 400°C to obtain a deformed multi-element alloy material.

[0060] Performance Testing

[0061] (1) The metallographic morphology of the medical degradable magnesium-based composite alloy materials obtained in Examples 1 to 3 and the multi-component alloy material obtained in Comparative Example 3 is shown in FIG. Figure 1 As shown, Figure 1 The scale bar in the figure is 100 μm. Figure 1In the figure, a is the multi-element alloy material of Comparative Example 3, b is the medical degradable magnesium-based composite alloy material obtained by 3 rolling passes of Example 1, c is the medical degradable magnesium-based composite alloy material obtained by 4 rolling passes of Example 2, and d is the medical degradable magnesium-based composite alloy material obtained by 5 rolling passes of Example 3.

[0062] The metallographic morphology results show that the metallographic structure of comparative example 3 presents typical deformation structure characteristics, that is, coarse grains, a large amount of second phases, and fast degradation. Compared with the multi-component alloy of comparative example 3, after 3 passes of rolling, the grain size of embodiment 1 is smaller; after 4 passes of rolling, the grain size of embodiment 2 is finer; after 5 passes of rolling, the grain size becomes larger than that of 3 and 4 passes, and is smaller than that of the multi-component alloy of comparative example 3.

[0063] (2) Mechanical experiments were carried out in accordance with GB / T 16865-2023. The tensile test stress-strain curves of the medical degradable magnesium-based composite alloy materials obtained in Examples 1 to 3 and the multi-element alloy material obtained in Comparative Example 3 are shown in FIG. Figure 2 The mechanical test results show that the yield strength σ of MCH-3 in Example 1 is 0.2 is 10.74MPa, and the tensile strength σ b is 135.33MPa, and the elongation is 1.84%; the yield strength σ of MCH-4 of Example 2 0.2 is 18.74MPa, and the tensile strength σ b is 189.36MPa, and the elongation is 2.33%; the yield strength σ of MCH-4 of Example 3 0.2 is 79.35MPa, and the tensile strength σ b is 175.74MPa, and the elongation is 0.87%; the yield strength σ of the multi-element alloy of Example 3 0.2 is 25.8MPa, and the tensile strength σ b It is 64.8MPa and the elongation is 0.34%.

[0064] (3) Mechanical experiments were carried out in accordance with GB / T 16865-2023. The tensile test stress-strain curves of the medical degradable magnesium-based composite alloy material obtained in Example 3 and the alloy materials of Comparative Examples 1 to 3 are as follows: Figure 3 The mechanical test results show that the yield strength σ of the alloy material of Example 1 0.2 is 23.09MPa, and the tensile strength σ b The yield strength of the alloy material of Comparative Example 2 is 105.98 MPa, and the elongation is 8.67%. 0.2 is 18.16MPa, and the tensile strength σ b It is 70.05MPa and the elongation is 5.65%.

[0065] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a medical degradable magnesium-based composite alloy material, comprising the following steps: The metal powders are mixed and plastic processed under heating conditions to obtain a medical degradable magnesium-based composite alloy material; The metal powder includes a plurality of binary magnesium alloy powders, or includes a plurality of binary alloy powders and high-purity magnesium powder; The binary magnesium alloy powder is selected from two or more of Mg-Cu alloy, Mg-Ca alloy, Mg-Sr alloy, Mg-Zn alloy and Mg-Mn alloy; The plastic processing is one or more of extrusion, rolling and forging.

2. The preparation method according to claim 1, characterized in that: The mass content of the functional element in the binary magnesium alloy is 0-5% and is not zero.

3. The preparation method according to claim 1 or 2, characterized in that: The particle size of the binary magnesium alloy powder is 1 μm to 1 mm.

4. The preparation method according to claim 1, characterized in that: The heating condition is a temperature of 150 to 500°C.

5. The preparation method according to claim 1, characterized in that: The extrusion ratio of the extrusion is 5 to 20:

1.

6. The preparation method according to claim 1, characterized in that: The rolling is performed in n passes, where n≥1; the deformation amount of the first pass of the rolling is ≥30%, and the deformation amount of each subsequent pass is 10-20%.

7. The preparation method according to claim 1, characterized in that: The forging temperature is 150-450° C., the forging pass is ≥1, and the deformation amount of a single pass is ≥10%.

8. The preparation method according to claim 1, characterized in that: Before the plastic processing, the mixed metal powder is cold pressed; The cold pressing pressure is 25-26 MPa and the time is 3 hours.

9. The medical degradable magnesium-based composite alloy material prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the medical degradable magnesium-based composite alloy material according to claim 9 in the preparation of medical implant materials.

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