A composite magnesium alloy material for periodically releasing functional ions, its preparation method and applications

Abstract

The present invention provides a composite magnesium alloy material capable of periodically releasing functional ions, a preparation method thereof, and an application thereof, belonging to the technical field of alloy materials. By alternately stacking magnesium plates and magnesium-zinc alloy plates and adopting the method of multiple rolling-folding-rolling, a composite magnesium alloy material with alternately arranged multiple magnesium layers and magnesium-zinc alloy layers can be obtained, thereby realizing the periodic release of zinc ions, regulating the corrosion and degradation rate of the composite magnesium alloy material in vivo, avoiding too fast corrosion and degradation rate, and also avoiding the negative biological effects caused by too high local zinc ion concentration. At the same time, by alternately stacking the magnesium layer and the magnesium-zinc alloy layer, the obtained composite magnesium alloy material has excellent mechanical properties, a wide range of applications, and high practical use value.

Description

Technical Field

[0001] The present invention relates to the technical field of alloy materials, and particularly relates to a composite magnesium alloy material that periodically releases functional ions, and a preparation method and application thereof. Background Art

[0002] Since the 21st century, problems such as population aging, frequent traffic accidents, and improper exercise injuries have emerged, which have attracted great attention to biomedical materials for body tissue and bone repair.

[0003] Magnesium is one of the essential elements for human life and participates in almost all life activities of the human body. Therefore, alloy materials with magnesium as the main component have attracted current medical attention. Magnesium and magnesium alloys have special advantages as medical implant materials - biodegradability. After magnesium corrodes in the human body, its products will not cause harm to the human body, meeting the biocompatibility characteristics required by biomaterials. Secondly, the density of magnesium is similar to that of human bone. As a repair material implanted in the human body, it can effectively stimulate bone growth and healing. Adding a part of zinc element to the magnesium alloy can increase the degradation rate of the magnesium alloy.

[0004] The existing medical magnesium-zinc alloy is Mg-6Zn alloy. However, when it is directly used as a medical bone repair material, its corrosion and degradation rate in the body is too fast, which easily leads to too high a local zinc ion concentration, thus producing negative biological effects. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a composite magnesium alloy material that periodically releases functional ions, and a preparation method and application thereof. The composite magnesium alloy material obtained by the present invention can release zinc ions periodically, promote bone tissue repair, and at the same time avoid negative biological effects caused by too high a local zinc ion concentration.

[0006] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a preparation method for a composite magnesium alloy material that periodically releases functional ions, comprising the following steps:

[0008] Stack magnesium plates and magnesium-zinc alloy plates alternately to obtain multiple stacked plates; the zinc content of the magnesium-zinc alloy plates is 1-4 wt%.

[0009] Perform the first high-temperature rolling on the multiple stacked plates to obtain a first composite plate;

[0010] Fold the first composite plate, and perform the second high-temperature rolling on the folded plate to obtain a second composite plate,... Repeat the steps of folding and high-temperature rolling multiple times to obtain a composite magnesium alloy material that periodically releases functional ions.

[0011] Preferably, the number of layers of the multiple sheets stacked is 2 to 8 layers.

[0012] Preferably, the thickness of a single magnesium sheet is 0.1 to 1 mm;

[0013] The thickness of a single magnesium-zinc alloy sheet is 0.1 to 1 mm.

[0014] Preferably, the temperature of each high-temperature rolling is 250 to 450 °C.

[0015] Preferably, the reduction per pass of each high-temperature rolling is 30 to 60%.

[0016] Preferably, the number of repetitions of the folding and high-temperature rolling is 2 to 6 times.

[0017] The present invention provides a composite magnesium alloy material capable of periodically releasing functional ions prepared by the above preparation method, including alternately stacked magnesium layers and magnesium-zinc alloy layers;

[0018] The total number of layers of the magnesium layers and the magnesium-zinc alloy layers is 10 to 100 layers.

[0019] Preferably, the thickness of the composite magnesium alloy material capable of periodically releasing functional ions is 0.2 to 2 mm.

[0020] The present invention provides an application of the above composite magnesium alloy material capable of periodically releasing functional ions in the preparation of bone repair materials.

[0021] The present invention provides a preparation method of a composite magnesium alloy material capable of periodically releasing functional ions, including the following steps: alternately stacking magnesium sheets and magnesium-zinc alloy sheets to obtain multiple stacked sheets; the zinc content of the magnesium-zinc alloy sheets is 1 to 4 wt%; performing the first high-temperature rolling on the multiple stacked sheets to obtain a first composite sheet; folding the first composite sheet, and performing the second high-temperature rolling on the folded sheet to obtain a second composite sheet,... repeating the steps of folding and high-temperature rolling multiple times to obtain a composite magnesium alloy material capable of periodically releasing functional ions. By alternately stacking magnesium sheets and magnesium-zinc alloy sheets and through the method of multiple rolling-folding-rolling, the present invention can obtain a composite magnesium alloy material with alternately arranged multiple magnesium layers and magnesium-zinc alloy layers, thereby realizing the periodic release of zinc ions, regulating the corrosion and degradation rate of the composite magnesium alloy material in vivo, avoiding too fast corrosion and degradation rate, and also avoiding the negative biological effects caused by too high local zinc ion concentration. At the same time, by alternately stacking the magnesium layers and the magnesium-zinc alloy layers, the obtained composite magnesium alloy material has excellent mechanical properties, a wide application range, and high practical use value.

[0022] Meanwhile, the preparation method provided by the present invention is simple in operation, low in cost, and easy to realize industrial mass production. Description of the Drawings

[0023] Figure 1 It is a schematic structural diagram of a composite magnesium alloy material for periodically releasing functional ions;

[0024] Figure 2 It is a cross-sectional metallographic diagram of the composite magnesium alloy plate obtained in Example 1;

[0025] Figure 3 It is the data of the Vickers hardness value of each layer of the composite magnesium alloy plate obtained in Example 1;

[0026] Figure 4 It is a cross-sectional metallographic diagram of the composite magnesium alloy plate obtained in Example 2;

[0027] Figure 5 It is the data of the Vickers hardness value of each layer of the composite magnesium alloy plate obtained in Example 2;

[0028] Figure 6 It is a comparison diagram of the tensile curves of the composite magnesium alloy plates obtained in Examples 1-2 and Comparative Examples 1-3. Detailed Embodiments

[0029] The present invention provides a preparation method of a composite magnesium alloy material for periodically releasing functional ions, comprising the following steps:

[0030] The magnesium plates and magnesium-zinc alloy plates are alternately stacked to obtain multiple stacked plates; the zinc content of the magnesium-zinc alloy plates is 1-4 wt%;

[0031] The multiple stacked plates are subjected to a first high-temperature rolling to obtain a first composite plate;

[0032] The first composite plate is folded in half, and the folded plate is subjected to a second high-temperature rolling to obtain a second composite plate,... The steps of folding in half and high-temperature rolling are repeated multiple times to obtain a composite magnesium alloy material for periodically releasing functional ions.

[0033] In the present invention, the magnesium plates and magnesium-zinc alloy plates are alternately stacked to obtain multiple stacked plates. In the present invention, the material of the magnesium plates is preferably high-purity magnesium, and the purity of the high-purity magnesium is preferably ≥99.98%. In the present invention, the thickness of a single magnesium plate is preferably 0.1-1 mm, more preferably 0.3-0.6 mm.

[0034] In the present invention, the zinc content of the magnesium-zinc alloy plates is 1-4 wt%, preferably 2-3 wt%, and the balance is magnesium. In the present invention, the thickness of a single magnesium-zinc alloy plate is preferably 0.1-1 mm, more preferably 0.3-0.6 mm.

[0035] The present invention preferably pre-treats the magnesium sheet and the magnesium-zinc alloy sheet. The pre-treatment preferably includes grinding, polishing, cleaning, and drying carried out in sequence. In the present invention, the grinding method is preferably to grind the surface with sandpaper from coarse to fine until there is no oxide scale on the surface; the polishing method is preferably to chemically polish the magnesium-zinc alloy sheet with a solution of phosphoric acid + ethylene glycol at 55 ± 5 °C, and the volume ratio of phosphoric acid to ethylene glycol is preferably 2:3; in the present invention, the detergent used for cleaning is preferably ethanol, purified water, ethanol, and ethanol solution, the cleaning is preferably ultrasonic cleaning, and the number of cleaning times is multiple; through the multiple cleaning in the present invention, the residue of the polishing solution is prevented; in the present invention, the drying is preferably drying by baking.

[0036] In the present invention, the number of layers of the multiple sheets stacked is 2 to 8 layers, preferably 3 to 5 layers.

[0037] After obtaining the multiple sheets stacked, the present invention performs the first hot rolling on the multiple sheets stacked to obtain a first composite sheet. In the present invention, the temperature of the first hot rolling is preferably 250 to 450 °C, more preferably 300 to 400 °C, and further preferably 350 °C. In the present invention, the pass reduction of the first hot rolling is preferably 30 to 60%, more preferably 40 to 50%.

[0038] After obtaining the first composite sheet, the present invention folds the first composite sheet in half, and performs the second hot rolling on the folded sheet to obtain a second composite sheet,... repeating the steps of folding in half and hot rolling multiple times to obtain a composite magnesium alloy material that periodically releases functional ions. In the present invention, the folding method is preferably to fold along the midline. Through the folding in the present invention, the number of layers of the composite sheet is doubled.

[0039] In the present invention, the temperature of the second hot rolling is preferably 250 to 450 °C, more preferably 300 to 400 °C, and further preferably 350 °C. In the present invention, the pass reduction of the second hot rolling is preferably 30 to 60%, more preferably 40 to 50%.

[0040] In the present invention, the number of repetitions of folding in half and hot rolling is preferably 2 to 6 times, more preferably 3 to 5 times.

[0041] The present invention provides a composite magnesium alloy material that periodically releases functional ions prepared by the above preparation method, including alternately stacked magnesium layers and magnesium-zinc alloy layers. In the present invention, the total number of layers of the magnesium layer and the magnesium-zinc alloy layer is 10 to 100 layers, preferably 20 to 80 layers, and more preferably 30 to 50 layers.

[0042] In the present invention, the thickness of the composite magnesium alloy material that periodically releases functional ions is preferably 0.2 - 2 mm, more preferably 0.5 - 1.5 mm, and further preferably 0.8 - 1.2 mm.

[0043] In the present invention, the thicknesses of the single-layer magnesium layer and the magnesium-zinc alloy layer are independently preferably 4 - 40 μm, more preferably 10 - 30 μm.

[0044] In the present invention, the schematic structural diagram of the composite magnesium alloy material that periodically releases functional ions is as Figure 1 shown.

[0045] The present invention provides the application of the above-mentioned composite magnesium alloy material that periodically releases functional ions in the preparation of bone repair materials. In the present invention, the composite magnesium alloy material that periodically releases functional ions is preferably a bone plate material.

[0046] The following will describe in detail the composite magnesium alloy material that periodically releases functional ions provided by the present invention, its preparation method and application with reference to embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0047] Example 1

[0048] Prepare 2 high-purity magnesium plates (purity 99.98%, zinc content 0), 2 magnesium-zinc alloy plates with a zinc content of 1 wt%, polish, clean and dry the high-purity magnesium plates and magnesium-zinc alloy plates to remove the oxide layer on the plate surface.

[0049] Stack the above high-purity magnesium plates and magnesium-zinc alloy plates alternately, perform the first high-temperature rolling (4 layers) on the alternately stacked multi-layer plates at a temperature of 350°C and a pass deformation of 50%, then fold it in half, perform the second high-temperature rolling (8 layers) on the folded plate at a temperature of 350°C and a pass deformation of 50%, and perform the third high-temperature rolling (16 layers) on the folded plate at a temperature of 350°C and a pass deformation of 50% to obtain a composite magnesium alloy plate that periodically releases functional ions (hereinafter referred to as the composite magnesium alloy plate for short), including alternately stacked high-purity magnesium layers and magnesium-zinc alloy layers, with a total of 16 layers, a thickness of 3.1 mm, and an average single-layer thickness of 0.19 mm.

[0050] Figure 2 is the cross-sectional metallographic diagram of the composite magnesium alloy plate obtained in Example 1 (scale 100 μm). It can be seen from the figure that the tissue stratification is obvious, with a total of 16 layers and good fusion; Figure 3 are the Vickers hardness value data of each layer of the composite magnesium alloy plate in Example 1. It can be seen that the hardness change of each layer shows a periodic change.

[0051] Example 2

[0052] Prepare 2 high-purity magnesium plates (purity: 99.98%, zinc content: 0) and 2 magnesium-zinc alloy plates with a zinc content of 0.5 wt%. Grind, polish, clean, and dry the high-purity magnesium plates and magnesium-zinc alloy plates to remove the oxide layer on the plate surface.

[0053] Stack the above high-purity magnesium plates and magnesium-zinc alloy plates alternately in layers, and perform the first hot rolling (4 layers) on the multi-layer plates stacked alternately at a temperature of 300°C and a pass reduction of 60%. Then fold it in half, and perform the second hot rolling (8 layers) on the folded plate at a temperature of 300°C and a pass reduction of 60%. Perform the third hot rolling (16 layers) on the folded plate at a temperature of 300°C and a pass reduction of 60% to obtain a composite magnesium alloy plate, including alternately stacked high-purity magnesium layers and magnesium-zinc alloy layers, with a total of 16 layers, a thickness of 2.1 mm, and an average single-layer thickness of 0.13 mm.

[0054] Figure 4 It is the cross-sectional metallographic diagram (scale: 100 μm) of the composite magnesium alloy plate obtained in Example 2. From Figure 4 it can be seen that the tissue stratification is obvious, with a total of 16 layers and good fusion. Figure 5 It is the Vickers hardness value data of each layer of the composite magnesium alloy plate in Example 2. It can be seen that the hardness change of each layer shows a periodic change.

[0055] Comparative Example 1

[0056] Use high-purity magnesium with a zinc content of 0 as a comparative example, and perform hot rolling on the plate with a two-high rolling mill at a temperature of 300°C and a one-pass reduction of 62.5% to obtain a magnesium material with a thickness of 3 mm.

[0057] Comparative Example 2

[0058] Use a magnesium-zinc alloy plate with a zinc content of 0.5% ( Figure 6 denoted as Z0.5 in

[0059] as a comparative example, and perform hot rolling on the plate with a two-high rolling mill at a temperature of 300°C and a one-pass reduction of 62.5% to obtain a magnesium-zinc alloy material with a thickness of 3 mm.

[0060] Use a magnesium-zinc alloy plate with a zinc content of 1.25% ( Figure 6 denoted as Z1.25 in

[0061] Figure 6 as a comparative example, and perform hot rolling on the plate with a two-high rolling mill at a temperature of 350°C and a one-pass reduction of 62.5% to obtain a magnesium-zinc alloy material with a thickness of 3 mm.It is a comparison chart of the tensile curves of the composite magnesium alloy plates obtained in Examples 1-2 and Comparative Examples 1-3. It can be seen from the chart that Example 1 well maintained the strength and plasticity of Z1.25, Example 2 basically maintained the strength and plasticity of Z0.5, and the strength of Example 1 and Example 2 was greatly improved compared with that of the pure magnesium plate by simple rolling.

[0062] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a composite magnesium alloy material for periodically releasing functional ions, wherein the composite magnesium alloy material for periodically releasing functional ions is used as a bone repair material; the preparation method of the composite magnesium alloy material for periodically releasing functional ions comprises the following steps: Prepare 2 high-purity magnesium plates with a purity of 99.98% and a zinc content of 0, and 2 magnesium-zinc alloy plates with a zinc content of 1 wt%. Grind, polish, clean, and dry the high-purity magnesium plates and the magnesium-zinc alloy plates to remove the oxide layer on the plate surface. Stack the high-purity magnesium plates and the magnesium-zinc alloy plates alternately, and perform the first hot rolling on the 4 stacked plates at a temperature of 350 °C and a pass reduction of 50%. Then fold it in half, perform the second hot rolling on the 8 folded plates at a temperature of 350 °C and a pass reduction of 50%. Then fold it in half again, and perform the third hot rolling on the 16 folded plates at a temperature of 350 °C and a pass reduction of 50% to obtain a composite magnesium alloy plate for periodically releasing functional ions. The composite magnesium alloy plate for periodically releasing functional ions comprises alternately stacked high-purity magnesium layers and magnesium-zinc alloy layers, with a total of 16 layers, a thickness of 3.1 mm, and an average single-layer thickness of 0.19 mm.

2. The composite magnesium alloy material for periodically releasing functional ions prepared by the preparation method according to claim 1, comprising alternately stacked high-purity magnesium layers and magnesium-zinc alloy layers, with a total of 16 layers, a thickness of 3.1 mm, and an average single-layer thickness of 0.19 mm. The composite magnesium alloy material for periodically releasing functional ions is used as a bone repair material.

3. Use of the composite magnesium alloy material for periodically releasing functional ions according to claim 2 in the preparation of a bone repair material.

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