Magnesium-based composite material, method for the production thereof, use thereof

Abstract

The application discloses a magnesium-based composite material and a preparation method and application thereof. The magnesium-based composite material comprises ferroferric oxide and a magnesium alloy. The magnesium alloy comprises the following components in percentage by weight: 3wt.%-6wt.% of Zn, 0.3wt.%-0.8wt.% of Ca, and the rest of Mg and inevitable impurities. The magnesium-based composite material can effectively solve the problem that micron-sized particles are easy to agglomerate in a metal liquid when the magnesium alloy is modified, and the plasticity of the alloy is reduced and the alloy is not easy to be formed.

Description

Technical Field

[0001] This application relates to the field of alloy materials, specifically to a magnesium-based composite material, a method for preparing the magnesium-based composite material, and the uses of the magnesium-based composite material. Background Technology

[0002] Magnesium alloys are excellent biomedical materials, characterized by good biocompatibility, safety, non-toxicity, and biodegradability. They have already demonstrated successful applications as implantable materials such as cardiovascular stents and bone screws. Furthermore, the microenvironment created during the biodegradation of magnesium alloys can inhibit tumor growth. Therefore, using magnesium alloys as magnetothermal media can exhibit a dual synergistic inhibitory effect on tumors through thermal ablation and the creation of a suitable microenvironment under magnetic induction heating, demonstrating excellent application prospects.

[0003] However, magnesium alloys are inherently non-magnetic, resulting in very low intrinsic heating efficiency. They require a large alternating magnetic field, which can heat normal human tissue, posing a significant safety hazard. Furthermore, current medical-grade magnesium alloys degrade slowly in vivo, often failing to achieve the desired tumor-suppressing effect.

[0004] Therefore, magnesium alloys can be modified by adding modified particles, enabling them to not only function as magnetothermal media but also to degrade rapidly in organisms. However, micron-sized particles often agglomerate in molten metal, leading to a significant decrease in the overall plasticity of the alloy and making it difficult to form and process. Therefore, it is necessary to design the composition of the alloy matrix and optimize the preparation process. Summary of the Invention

[0005] The purpose of this application is to provide a magnesium-based composite material that can effectively solve the problem that when micron-sized particles are modified into magnesium alloys, they tend to agglomerate in the molten metal, leading to a decrease in the plasticity of the alloy and making it difficult to form and process.

[0006] To achieve the above objectives, the technical solution of this application provides a magnesium-based composite material, the composition of which is iron(III) oxide and magnesium alloy, wherein the magnesium alloy comprises the following components by weight percentage: Zn 3wt.% to 6wt.%, Ca 0.3wt.% to 0.8wt.%, with the remainder being Mg and unavoidable impurities.

[0007] In some embodiments of this application, the magnesium alloy comprises the following components by weight percentage: Zn 3.0 wt.% to 5.8 wt.%, Ca 0.3 wt.% to 0.6 wt.%, with the remainder being Mg and unavoidable impurities.

[0008] In some embodiments of this application, the composition of the magnesium-based composite material, by weight, is: x parts of iron(III) oxide, where 0 < x ≤ 10, and the remainder is the magnesium alloy.

[0009] In some embodiments of this application, the particle size of the iron oxide is 1 micrometer to 50 micrometers.

[0010] The technical solution of this application also provides a method for preparing a magnesium-based composite material, which is used to prepare the above-mentioned magnesium-based composite material. The preparation method includes: heating pure magnesium, pure zinc and magnesium-calcium master alloy in a preset ratio to a first temperature under the protection of a protective gas, melting and mixing them to obtain a magnesium alloy melt, and cooling the magnesium alloy melt to a second temperature; adding iron(III) oxide preheated to a third temperature to the cooled magnesium alloy melt to obtain a magnesium-based composite material melt; casting the magnesium-based composite material melt into a mold to obtain a magnesium-based composite material ingot; homogenizing the magnesium-based composite material ingot and molding it to obtain the magnesium-based composite material.

[0011] In some embodiments of this application, the preset proportion is obtained through the following steps: calculating the solid-liquid phase temperature range of the magnesium-zinc-calcium ternary magnesium alloy using a thermodynamic ternary phase diagram; selecting a magnesium alloy composition that can generate the preset solid-liquid phase temperature range and has a second phase volume fraction of no more than 5%; and determining the preset proportion based on the magnesium alloy composition.

[0012] In some embodiments of this application, the preparation method satisfies at least one of the following conditions: a. the protective gas includes a mixture of carbon dioxide and sulfur hexafluoride or a mixture of argon and sulfur hexafluoride; b. the first temperature is 680℃~750℃; c. the second temperature is lower than the liquidus temperature of the zinc-calcium-magnesium ternary magnesium alloy, and the temperature difference is 20℃~50℃.

[0013] In some embodiments of this application, the preparation method satisfies at least one of the following conditions: A. The third temperature is 300℃~500℃; B. The stirring rate when adding the iron oxide is 300r / min~500r / min.

[0014] In some embodiments of this application, the preparation method satisfies at least one of the following conditions: (1) the homogenization treatment temperature is 300℃~400℃ and the time is 8 hours~20 hours; (2) the molding processing temperature is 250℃~350℃.

[0015] This application also provides the use of the aforementioned magnesium-based composite material as an implant material.

[0016] Compared with the prior art, the magnesium-based composite material and its preparation method of this application have the following beneficial effects:

[0017] The magnesium-based composite material of this application comprises a magnesium alloy with a specific composition: Zn 3wt.% to 6wt.%, Ca 0.3wt.% to 0.8wt.%, with the remainder being Mg and unavoidable impurities. This magnesium alloy with a specific composition has a large semi-solid solidification range and good ductility. Therefore, by using a semi-solid stirring molding method, micron-sized iron oxide particles can be easily and uniformly dispersed into the magnesium alloy, and the resulting magnesium-based composite material still has good plastic deformation ability and is easy to process and mold.

[0018] By introducing iron(III) oxide into magnesium alloys, the magnetic properties of the magnesium alloys are improved, thereby enabling the resulting magnesium-based composite materials to have a higher heating temperature under a lower alternating magnetic field strength. At the same time, due to the large potential difference between iron(III) oxide and the magnesium matrix, the magnesium-based composite materials exhibit a faster degradation rate in vivo. When this magnesium-based composite material is used as an implant material as a magnetocaloric induction medium, it can simultaneously exhibit a dual synergistic inhibitory effect on tumors through thermal ablation and microenvironment, showing excellent application prospects in the field of anti-tumor therapy.

[0019] The preparation method of the technical solution of this application designs the alloy raw material ratio by selecting alloy elements that can generate a large solid-liquid phase temperature range and whose second phase volume fraction does not exceed 5%, which can prepare magnesium-based composite materials that are both conducive to the uniform dispersion of iron oxide particles and have good plastic deformation ability. Attached Figure Description

[0020] The following accompanying drawings describe in detail the exemplary embodiments disclosed in this application. The same reference numerals denote similar structures in several views of the drawings. Those skilled in the art will understand that these embodiments are non-limiting and exemplary, and the drawings are for illustrative purposes only and are not intended to limit the scope of this application. Other embodiments may similarly fulfill the inventive intent of this application. It should be understood that the drawings are not drawn to scale. Wherein:

[0021] Figure 1 This is a scanning electron microscope image of the magnesium-based composite filament from Example 1;

[0022] Figure 2 The stress-strain curves of the magnesium-based composite wires in Examples 1, 2, and 1 are shown.

[0023] Figure 3 Here is a scanning electron microscope image of the magnesium-based composite filament from Example 2;

[0024] Figure 4 This is a scanning electron microscope image of the magnesium-based composite wire from Comparative Example 1. Detailed Implementation

[0025] The following description provides specific application scenarios and requirements for this application, intended to enable those skilled in the art to make and use the content of this application. Various partial modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of this application. Therefore, this application is not limited to the embodiments shown, but rather to the widest scope consistent with the claims.

[0026] During their research on anti-tumor materials, the inventors discovered that magnesium alloys can be modified with magnetic iron oxide (Fe3O4). This Fe3O4 enhances the magnetism of the magnesium alloy, significantly reducing the alternating magnetic field strength when used as a magnetothermal medium in implants. Furthermore, the large potential difference between Fe3O4 and the magnesium matrix results in a faster degradation rate of the modified magnesium alloy in vivo. Therefore, modifying magnesium alloys with Fe3O4 allows them to exhibit a dual synergistic inhibitory effect on tumors through both thermal ablation and microenvironmental regulation. However, because Fe3O4 particles are hard oxide particles, adding micron-sized Fe3O4 particles to magnesium alloys causes them to easily agglomerate in the molten magnesium alloy, significantly reducing the plasticity and processing performance of the modified magnesium alloy.

[0027] Based on this, the technical solution of this application designs the composition of the magnesium alloy matrix and designs a magnesium alloy with a specific composition. Since the magnesium alloy with this specific composition has a large semi-solid solidification range, it is easy to uniformly disperse micron-sized iron oxide particles into the magnesium alloy when using the semi-solid stirring molding method. At the same time, the magnesium alloy with this specific composition has good ductility. Even if micron-sized particles are added to the magnesium alloy with this specific composition, the resulting magnesium-based composite material still has good plastic deformation ability.

[0028] In one specific embodiment, the magnesium-based composite material is composed of iron oxide and magnesium alloy, wherein the magnesium alloy comprises the following components by weight percentage: Zn 3wt.% to 6wt.%, Ca 0.3wt.% to 0.8wt.%, with the remainder being Mg and unavoidable impurities, and the iron oxide has a good dispersion effect in the magnesium alloy.

[0029] For example, the weight percentage of Zn can be 3.0 wt.%, 3.1 wt.%, 3.2 wt.%, 3.3 wt.%, 3.4 wt.%, 3.5 wt.%, 3.6 wt.%, 3.7 wt.%, 3.8 wt.%, 3.9 wt.%, 4.0 wt.%, 4.1 wt.%, 4.2 wt.%, 4.3 wt.%, 4.4 wt.%, 4.5 wt.%, 4.6 wt.%, 4.7 wt.%, 4.8 wt.%, 4.9 wt.%, 5.0 wt.%, 5.1 wt.%, 5.2 wt.%, 5.3 wt.%, 5.4 wt.%, 5.5 wt.%, 5.6 wt.%, 5.7 wt.%, 5.8 wt.%, 5.9 wt.%, 6.0 wt.%, or any range or subrange between any two of these values. For example, the weight percentage of Ca can be 0.30 wt.%, 0.31 wt.%, 0.32 wt.%, 0.33 wt.%, 0.34 wt.%, 0.35 wt.%, 0.36 wt.%, 0.37 wt.%, 0.38 wt.%, 0.39 wt.%, 0.40 wt.%, 0.41 wt.%, 0.42 wt.%, 0.43 wt.%, 0.44 wt.%, 0.45 wt.%, 0.46 wt.%, 0.47 wt.%, 0.48 wt.%, 0.49 wt.%, 0.50 wt.%, 0.51 wt.%, 0.52 wt.%, 0.53 wt.%, 0.54 wt.%, and 0.55 wt.%. %, 0.56wt.%, 0.57wt.%, 0.58wt.%, 0.59wt.%, 0.60wt.%, 0.61wt.%, 0.62wt.%, 0.63wt.%, 0.64wt.%, 0.65wt.%, 0.66wt.%, 0.67wt.%, 0.68wt.%, 0.69wt.%, 0.70wt.%, 0.71wt.%, 0.72wt.%, 0.73wt.%, 0.74wt.%, 0.75wt.%, 0.76wt.%, 0.77wt.%, 0.78wt.%, 0.79wt.%, 0.80wt.%, or a range or subrange between any two of these values.

[0030] In a preferred embodiment, the magnesium alloy comprises the following components by weight percentage: Zn 3.0 wt.% to 5.8 wt.%, Ca 0.3 wt.% to 0.6 wt.%, with the remainder being Mg and unavoidable impurities.

[0031] Using a magnesium alloy with a specific composition (Zn 3wt.%–6wt.%, Ca 0.3wt.%–0.8wt.%, with the remainder being Mg and unavoidable impurities), the semi-solid solidification range of the magnesium alloy can be extended to over 200℃. Due to the high density of iron oxide particles, they easily agglomerate and settle to the bottom of the magnesium alloy melt during mixing, leading to cracking and failure in subsequent processing. However, when the magnesium alloy melt is in the semi-solid range, the alloy solid phase hinders the settling of added particles. Increasing the semi-solid temperature range allows for precise control of the solid and liquid phase content during stirring. This enables the easy and uniform dispersion of micron-sized iron oxide particles into the magnesium alloy matrix using a semi-solid stirring molding method, while also maintaining good plastic deformation capabilities.

[0032] In one specific embodiment, the magnesium-based composite material, by weight, comprises: x parts of iron(III) oxide, where 0 < x ≤ 10, and the remainder is magnesium alloy. For example, x can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, or a range or subrange between any two of these values.

[0033] In a preferred embodiment, the magnesium-based composite material comprises, by weight, 2 to 8 parts of iron(III) oxide and the remainder being magnesium alloy.

[0034] The size of the iron(III) oxide (Fe3O4) affects the processing performance of the magnesium-based composite material. If the particle size of the iron(III) oxide is too small, it is difficult to disperse in the magnesium alloy; if the particle size of the iron(III) oxide is too large, the magnesium-based composite material formed by the dispersion of iron(III) oxide in the aluminum alloy will have poor plasticity and be difficult to process and shape. In a preferred embodiment, the particle size of the iron(III) oxide is 1 micrometer (μm) to 50 micrometers (μm). For example, the particle size of the iron(III) oxide is 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm. m, 28μm, 29μm, 30μm, 31μm, 32μm, 33μm, 34μm, 35μm, 36μm, 37μm, 38μm, 39μm, 40μm, 41μm, 42μm, 43μm, 44μm, 45μm, 46μm, 47μm, 48μm, 49μm, 50μm, or a range or subrange between any two of these values.

[0035] This application also provides the use of the above-described magnesium-based composite material as an implant material. In some embodiments, the implant material can be used as an anti-tumor material, and the rapid degradation of the magnesium-based composite material can treat tumors or cancer. In some preferred embodiments, the degradation rate of the magnesium-based composite material in vivo is 100 mg / cm³. 2 / day ~200mg / cm 2 / day. In some embodiments, the implant material can be used as a magnetothermal induction medium, using an alternating magnetic field to magnetically induction heat the magnesium-based composite material to treat tumors or cancer.

[0036] In some preferred embodiments, when the magnesium-based composite material is used as an implant material as a magnetocaloric induction medium, the alternating magnetic field strength is 500 A / m to 1500 A / m, and the alternating frequency is 330 kHz to 430 kHz. Under this alternating magnetic field condition, the heating temperature of the magnesium-based composite material can be 60℃ to 80℃, which can not only directly ablate tumor cells or induce tumor cell apoptosis, but also avoid damage to other normal parts of the body, resulting in a high safety factor. In some more preferred embodiments, the alternating magnetic field strength is 1000 A / m, and the alternating frequency is 380 kHz.

[0037] It should be noted that when the magnesium-based composite material is used as an implant material and a magnetothermal induction medium to treat tumors or cancer, it can not only ablate tumor cells or induce tumor cell apoptosis through magnetic induction heating, but also inhibit tumor growth through the microenvironment created by its degradation in the body. The degradation rate of the magnesium-based composite material in the body is crucial. If the degradation rate is too high, it may degrade before the interventional treatment is completed, affecting the ablation effect. Conversely, if the degradation rate is too low, it will affect the tumor-inhibiting effect of the microenvironment created by the degradation of the magnesium-based composite material. Therefore, both excessively high and low degradation rates of the magnesium-based composite material in the body will affect the anti-tumor treatment effect. In this application, the embodiments are designed with appropriate amounts of iron(III) oxide and magnesium alloy to achieve a suitable degradation rate for the magnesium-based composite material in the body. In some preferred embodiments, the degradation rate of the magnesium-based composite material in the body is 100 mg / cm³. 2 / day ~200mg / cm 2 / sky.

[0038] In some specific embodiments, the tumor or cancer is selected from malignant tumors or cancers of the lungs, liver and gallbladder, gastrointestinal tract, hematologic malignancies, sarcomas, skin, bones, genitourinary tract, nervous system, gynecological conditions, and adrenal glands. Preferably, the malignant tumor or cancer of the lungs is selected from bronchial carcinoma (squamous cell carcinoma, undifferentiated small cell, undifferentiated large cell, or adenocarcinoma), non-small cell lung cancer, bronchial carcinoma, bronchial adenoma, sarcoma, lymphoma, chondromatosis, or mesothelioma. The malignant tumor or cancer of the liver and gallbladder is selected from liver cancer, bile duct cancer, hepatoblastoma, angiosarcoma, hepatocellular adenoma, hemangioma, gallbladder cancer, ampullary cancer, or bile duct cancer. The gastrointestinal malignancies or cancers are selected from esophageal malignancies or cancers (squamous cell carcinoma, adenocarcinoma, leiomyosarcoma, or lymphoma), gastric malignancies or cancers (carcinoma, lymphoma, or leiomyosarcoma), pancreatic malignancies or cancers (ductal adenocarcinoma, insulinoma, glucagonoma, gastrinoma, carcinoid tumor, uveaoma), small intestine (adenocarcinoma, lymphoma, carcinoid, Kaposi's sarcoma, leiomyoma, hemangioma, lipoma, neurofibroma, fibroma), colorectal malignancies or cancers (adenocarcinoma, adenoma, adenoma, tubular adenoma), or leiomyomas. The hematologic malignancies or cancers are selected from acute or chronic myeloid leukemia, acute lymphoblastic leukemia, chronic lymphocytic leukemia, myeloproliferative disorders, multiple myeloma, myelodysplastic syndromes, Hodgkin's disease, or non-Hodgkin's lymphoma. The sarcoma is selected from angiosarcoma, fibrosarcoma, rhabdomyosarcoma, liposarcoma, myxoma, rhabdomyosarcoma, fibroma, lipoma, or teratoma. The malignant skin tumor or cancer is selected from malignant melanoma, basal cell carcinoma, squamous cell carcinoma, Kaposi's sarcoma, nevus, hyperplastic nevus, lipoma, hemangioma, dermatofibroma, keloid, or psoriasis. The malignant bone tumor or cancer is selected from osteosarcoma, fibrosarcoma, malignant fibrous histiocytoma, chondrosarcoma, Ewing's sarcoma, malignant lymphoma, multiple myeloma, malignant giant cell tumor chordoma, osteochondroma, benign chondroma, chondroblastoma, chondromyomas, osteofibroma, osteoid osteoma, or giant cell tumor. The malignant tumors or cancers of the genitourinary tract are selected from malignant tumors or cancers of the kidneys (adenocarcinoma, Wilms' tumor, or nephroblastoma), lymphoma, leukemia, malignant tumors or cancers of the bladder or urethra (squamous cell carcinoma, transitional cell carcinoma, or adenocarcinoma), malignant tumors or cancers of the prostate (adenocarcinoma or sarcoma), malignant tumors or cancers of the testes (leukemia, teratoma, embryonal carcinoma, or teratoma), choriocarcinoma, sarcoma, stromal cell carcinoma, fibroma, fibroadenoma, adenoma-like tumor, or lipoma.The malignant tumors or cancers of the nervous system are selected from osteoma, hemangioma, granuloma, xanthoma, osteitis deformans, meningioma, meningeal sarcoma, glioma, astrocytoma, medulloblastoma, glioma, ependymoma, genital tumor, glioblastoma multiforme, oligodendroglioma, schwannoma, retinoblastoma, congenital tumor, spinal neurofibroma, meningioma, glioma, or sarcoma. The gynecological malignant tumors or cancers are selected from endometrial cancer (serous cystadenocarcinoma, mucinous cystadenocarcinoma, or unclassified carcinoma), granulosa-schwannoma, testicular stromal cell tumor, myometrial aberration, malignant teratoma, squamous cell carcinoma, fibroepithelial carcinoma, adenocarcinoma, melanoma, clear cell carcinoma, squamous cell carcinoma, botryoid sarcoma, or fallopian tube cancer. The adrenal malignant tumors or cancers are selected from neuroblastoma.

[0039] This application also provides a method for preparing the above-mentioned magnesium-based composite material. In some specific embodiments, the preparation method includes the following steps:

[0040] S1: Pure magnesium, pure zinc and magnesium-calcium master alloy in a preset ratio are heated to a first temperature under the protection of a protective gas, melted and mixed to obtain a magnesium alloy melt, and the magnesium alloy melt is cooled to a second temperature.

[0041] S2: Add the preheated iron(III) oxide to the cooled magnesium alloy melt to obtain a magnesium-based composite material melt;

[0042] S3: The magnesium-based composite material melt is poured into a mold to obtain a magnesium-based composite material ingot;

[0043] S4: The magnesium-based composite material ingot is homogenized and then formed to obtain the magnesium-based composite material.

[0044] In some specific embodiments, in step S1, the preset ratio is obtained through the following steps:

[0045] S11: Calculate the solid-liquid phase temperature range and phase composition of magnesium-zinc-calcium ternary magnesium alloy using a thermodynamic ternary phase diagram;

[0046] S12: Select a magnesium alloy composition that can generate a preset solid-liquid phase temperature range and a second phase volume fraction of no more than 5%.

[0047] S13: Determine the preset ratio based on the magnesium alloy composition.

[0048] In step S11, based on the existing ternary phase diagram of magnesium-zinc-calcium ternary magnesium alloy, the phase composition of Mg-xZn-yCa at different temperatures is determined, where x represents the weight percentage of Zn in the magnesium alloy and y represents the weight percentage of Ca in the magnesium alloy, and y is 0.3wt.% to 0.8wt.%. In this step, the value of y can be fixed first, for example, fixed at 0.5wt.%. The temperature at which the solid phase begins to precipitate from the liquid phase during solidification is the liquidus line, and the temperature at which the liquid phase completely solidifies into the solid phase is the solidus line, thereby determining the solid-liquid phase temperature range.

[0049] In step S12, thermodynamic calculations revealed that adding 1 wt.% Zn effectively expands the solid-liquid phase temperature range. When the Zn content is greater than or equal to 3 wt.%, the solid-liquid phase temperature range exceeds 150°C. When the Zn content exceeds 6 wt.%, the volume fraction of the second phase exceeds 5%. Excessive second phase is detrimental to the alloy's ductility; therefore, x is 3 wt.% to 6 wt.%. Furthermore, since calcium can form atomic segregations with zinc, leading to a decrease in structural strength, the alloy can retain a high elongation.

[0050] In step S13, based on the magnesium alloy composition selected in step S12, the proportions of pure magnesium, pure zinc, and magnesium-calcium master alloy are designed. In some specific embodiments, the calcium weight percentage in the magnesium-calcium master alloy is 30 wt.%.

[0051] Since the magnesium alloy composition selected in step S12 is designed based on the content of alloying elements that can generate a large solid-liquid phase temperature range and the volume fraction of the second phase does not exceed 5%, the ratio of pure magnesium, pure zinc and magnesium-calcium master alloy designed in step S13 based on the magnesium alloy composition selected in step S12 can prepare a magnesium-based composite material that is both conducive to the uniform dispersion of iron oxide particles and has good plastic deformation ability.

[0052] In some specific embodiments, the protective gas includes a mixture of carbon dioxide and sulfur hexafluoride or a mixture of argon and sulfur hexafluoride.

[0053] In some specific embodiments, the first temperature is 680℃~750℃. In some specific embodiments, the second temperature is lower than the solidus temperature of the zinc-calcium-magnesium ternary magnesium alloy, and the temperature difference is 20℃~50℃. Cooling down to this temperature range can make the magnesium alloy melt semi-solid.

[0054] In some specific embodiments, in step S2, the third temperature is 300℃ to 500℃ to avoid a sharp drop in the temperature of the magnesium alloy melt due to a large temperature difference caused by the added particles. The iron(III) oxide is added under stirring conditions to ensure that it is uniformly dispersed in the magnesium alloy melt. In some specific embodiments, the stirring rate when adding the iron(III) oxide is 300 r / min to 500 r / min.

[0055] In some specific embodiments, the homogenization treatment temperature is 300℃~400℃, and the time is 8 hours~20 hours. If the homogenization treatment temperature is too low, it will result in an excessive amount of second phase in the magnesium alloy, reducing the elongation of the alloy; if the homogenization treatment temperature is too high, it will result in an excessively large grain size in the magnesium alloy, thereby reducing the alloy strength. In some specific embodiments, the forming process temperature is 250℃~350℃ to avoid the wire failing to extrude or melting.

[0056] In some preferred embodiments, the molding process is hot extrusion molding, and the resulting magnesium-based composite material is a filament. Filament materials are more suitable for clinical interventional treatments that require implantation into lesions. In some preferred embodiments, the diameter of the magnesium-based composite material formed by hot extrusion molding is 1 mm to 2 mm.

[0057] The technical solution of this application will be clearly and completely described below with reference to the embodiments of this application. Unless otherwise specified, the reagents and raw materials used can be purchased commercially. Experimental methods in the following embodiments that do not specify specific conditions are performed according to conventional methods and conditions, or according to the product instructions.

[0058] In the following embodiments, scanning electron microscope (SEM) images were characterized using a Tesken GAIA3 SEM. Tensile tests were performed using wire samples with a diameter of 1.5 mm and a measurement length of 30 mm to obtain stress-strain curves. The testing equipment was an Instron 5982.

[0059] Example 1

[0060] By weight, the magnesium-based composite material of this embodiment consists of 5 parts of iron oxide particles with a particle size of 20 micrometers and 95 parts of magnesium alloy, wherein the magnesium alloy comprises the following components by weight percentage: Zn 5.79wt.%, Ca 0.47wt.%, with the remainder being Mg and unavoidable impurities.

[0061] The preparation method of the magnesium-based composite material in this embodiment includes the following steps:

[0062] (1) By weight, 88 parts of pure magnesium, 5.5 parts of pure zinc and 1.5 parts of magnesium-30wt.% calcium master alloy were heated to 700°C under the protection of a mixed gas of carbon dioxide and sulfur hexafluoride (volume ratio of 50:1) to obtain magnesium alloy melt. The magnesium alloy melt was then cooled to 550°C to form a semi-solid slurry.

[0063] (2) Stir the semi-solid slurry at a rate of 350 r / min using a stirring paddle, and add iron oxide particles preheated to 400℃ into the semi-solid slurry to obtain magnesium-based composite material melt.

[0064] (3) The magnesium-based composite material melt is poured into a mold to obtain a magnesium-based composite material ingot;

[0065] (4) The magnesium-based composite material ingot is homogenized at a temperature of 400°C for 12 hours. The homogenized magnesium-based composite material ingot is then hot-extruded at 300°C to obtain a continuous magnesium-based composite material wire with a diameter of 1.5 mm.

[0066] The scanning electron microscope image of the magnesium-based composite filament in this embodiment is shown below. Figure 1 , Figure 1 The white substance in the image is iron(III) oxide (Fe3O4). As shown in the figure, the iron(III) oxide particles are evenly distributed within the magnesium matrix.

[0067] The stress-strain curve of the magnesium-based composite wire in this embodiment is as follows: Figure 2 As shown, the magnesium-based composite filament has a yield strength of 135 MPa and an elongation at break of 6%, exhibiting good plastic deformation capacity.

[0068] Example 2

[0069] By weight, the magnesium-based composite material of this embodiment consists of 5 parts of iron oxide particles with a particle size of 20 micrometers and 95 parts of magnesium alloy, wherein the magnesium alloy comprises the following components by weight percentage: Zn 3.16wt.%, Ca 0.32wt.%, with the remainder being Mg and unavoidable impurities.

[0070] The preparation method of the magnesium-based composite material in this embodiment includes the following steps:

[0071] (1) By weight, 91 parts of pure magnesium, 3 parts of pure zinc and 1 part of magnesium-30wt.% calcium master alloy were heated to 700°C under the protection of a mixed gas of carbon dioxide and sulfur hexafluoride (volume ratio of 50:1) to obtain magnesium alloy melt after the raw materials were melted and mixed. The magnesium alloy melt was then cooled to 550°C to form a semi-solid slurry.

[0072] (2) Stir the semi-solid slurry at a rate of 350 r / min using a stirring paddle, and add iron oxide particles preheated to 400℃ into the semi-solid slurry to obtain magnesium-based composite material melt.

[0073] (3) The magnesium-based composite material melt is poured into a mold to obtain a magnesium-based composite material ingot;

[0074] (4) The magnesium-based composite material ingot is homogenized at the same temperature and time as in Example 1. The homogenized magnesium-based composite material ingot is hot-extruded at 300°C to obtain a continuous magnesium-based composite material wire with a diameter of 1.5 mm.

[0075] Figure 3 This is a scanning electron microscope (SEM) image of the magnesium-based composite filament of this embodiment. As can be seen from the image, in the magnesium-based composite filament of this embodiment, iron oxide particles are uniformly distributed in the magnesium alloy matrix.

[0076] The stress-strain curve of the magnesium-based composite wire in this embodiment is as follows: Figure 2 As shown in the figure, the yield strength of the magnesium-based composite wire in this embodiment is 130 MPa, and the elongation at break is 7%, indicating good plastic deformation capability. Comparing Examples 1 and 2, when the zinc and calcium content in the magnesium alloy decreases, the yield strength of the magnesium-based composite material decreases, while the elongation at break increases.

[0077] Comparative Example 1

[0078] By weight, the magnesium-based composite material of this comparative example consists of 5 parts of iron oxide particles with a particle size of 20 micrometers and 95 parts of magnesium alloy, wherein the magnesium alloy comprises the following components by weight percentage: Zn 1.05wt.%, Ca 0.32wt.%, with the remainder being Mg and unavoidable impurities.

[0079] The preparation method of the magnesium-based composite material in this comparative example includes the following steps:

[0080] (1) By weight, 93 parts of pure magnesium, 1 part of pure zinc and 1 part of magnesium-30wt.% calcium master alloy were heated to 700°C under the protection of a mixed gas of carbon dioxide and sulfur hexafluoride (volume ratio of 50:1) to obtain magnesium alloy melt after the raw materials were melted and mixed. The magnesium alloy melt was then cooled to 550°C to form a semi-solid slurry.

[0081] (2) Stir the semi-solid slurry at a rate of 350 r / min using a stirring paddle, and add iron oxide particles preheated to 400℃ into the semi-solid slurry to obtain magnesium-based composite material melt.

[0082] (3) The magnesium-based composite material melt is poured into a mold to obtain a magnesium-based composite material ingot;

[0083] (4) The magnesium-based composite material ingot was homogenized at the same temperature and time as in Example 1. The homogenized magnesium-based composite material ingot was hot-extruded at 300°C, but a continuous magnesium-based composite material wire with a diameter of 1.5 mm could not be obtained.

[0084] Figure 4 A scanning electron microscope (SEM) image of the magnesium-based composite filament of this comparative example is shown. Figure 4 As shown, in the magnesium-based composite wire of Comparative Example 1, the iron oxide particles exhibit severe agglomeration (refer to the area indicated by the white arrow in the figure).

[0085] The stress-strain curve of the magnesium-based composite wire in this comparative example is shown below. Figure 2 As shown in the figure, the yield strength of the magnesium-based composite wire in Comparative Example 1 is 140 MPa, and the elongation at break is 2%, indicating poor plastic deformation capacity. This is because the Zn content in the magnesium alloy composition of Comparative Example 1 is too low, resulting in insufficient semi-solid region of the magnesium alloy. This leads to severe agglomeration of iron oxide particles, ultimately resulting in poor plasticity of the magnesium-based composite material, making it impossible to hot extrude into continuous wire.

[0086] The above description of the embodiments is intended to enable those skilled in the art to understand and apply this application. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without creative effort. Therefore, this application is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of this application without departing from the scope and spirit of this application are within the scope of this application.

Claims

1. A magnesium-based composite material, characterized in that, The magnesium-based composite material is composed of iron oxide and magnesium alloy, wherein the magnesium alloy comprises the following components by weight percentage: Zn 3wt.%~6wt.%, Ca 0.3wt.%~0.8wt.%, with the remainder being Mg and unavoidable impurities; Based on 100 parts by weight, the composition of the magnesium-based composite material is: x parts of iron(III) oxide, where 0 < x ≤ 10, and the remainder is the magnesium alloy; The particle size of the iron oxide is 1 micrometer to 50 micrometers; The magnesium-based composite material was prepared by the following method: Pure magnesium, pure zinc, and magnesium-calcium master alloy in a preset ratio are heated to a first temperature under the protection of a protective gas, and after melting and mixing, a magnesium alloy melt is obtained. The magnesium alloy melt is then cooled to a second temperature. The second temperature is lower than the liquidus temperature of the zinc-calcium-magnesium ternary magnesium alloy, and the temperature difference is 20℃~50℃. Adding preheated iron oxide to a third temperature to the cooled magnesium alloy melt yields a magnesium-based composite material melt. The magnesium-based composite material melt is poured into a mold to obtain a magnesium-based composite material ingot; The magnesium-based composite material ingot is homogenized and then formed to obtain the magnesium-based composite material.

2. The magnesium-based composite material according to claim 1, characterized in that, The magnesium alloy comprises the following components by weight percentage: Zn 3.0wt.%~5.8wt.%, Ca 0.3wt.%~0.6wt.%, with the remainder being Mg and unavoidable impurities.

3. A method for preparing a magnesium-based composite material, characterized in that, The preparation method for the magnesium-based composite material according to any one of claims 1 to 2 comprises: Pure magnesium, pure zinc, and magnesium-calcium master alloy in a preset ratio are heated to a first temperature under the protection of a protective gas, and after melting and mixing, a magnesium alloy melt is obtained. The magnesium alloy melt is then cooled to a second temperature. The second temperature is lower than the liquidus temperature of the zinc-calcium-magnesium ternary magnesium alloy, and the temperature difference is 20℃~50℃. Adding preheated iron oxide to a third temperature to the cooled magnesium alloy melt yields a magnesium-based composite material melt. The magnesium-based composite material melt is poured into a mold to obtain a magnesium-based composite material ingot; The magnesium-based composite material ingot is homogenized and then formed to obtain the magnesium-based composite material.

4. The method for preparing the magnesium-based composite material according to claim 3, characterized in that, The preset ratio is obtained through the following steps: The solid-liquid phase temperature range and phase composition of magnesium-zinc-calcium ternary magnesium alloy were calculated using a thermodynamic ternary phase diagram. Magnesium alloy composition that can generate a preset solid-liquid phase temperature range and whose second phase volume fraction does not exceed 5% is selected. The preset ratio is determined based on the magnesium alloy composition.

5. The method for preparing the magnesium-based composite material according to claim 3, characterized in that, The preparation method must satisfy at least one of the following conditions: a. The protective gas includes a mixture of carbon dioxide and sulfur hexafluoride or a mixture of argon and sulfur hexafluoride; b. The first temperature is 680℃~750℃.

6. The method for preparing the magnesium-based composite material according to claim 3, characterized in that, The preparation method must satisfy at least one of the following conditions: A. The third temperature is 300℃~500℃; B. The stirring speed when adding the iron(III) oxide is 300 r / min to 500 r / min.

7. The method for preparing the magnesium-based composite material according to claim 3, characterized in that, The preparation method must satisfy at least one of the following conditions: (1) The homogenization treatment is carried out at a temperature of 300℃~400℃ for 8 hours~20 hours; (2) The temperature of the molding process is 250℃~350℃.

8. Use of the magnesium-based composite material according to any one of claims 1 to 2 as an implant material.

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