CN112981201A - Magnesium-zinc-calcium alloy and magnesium-zinc-calcium alloy powder - Google Patents
Magnesium-zinc-calcium alloy and magnesium-zinc-calcium alloy powder Download PDFInfo
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- CN112981201A CN112981201A CN201911297867.7A CN201911297867A CN112981201A CN 112981201 A CN112981201 A CN 112981201A CN 201911297867 A CN201911297867 A CN 201911297867A CN 112981201 A CN112981201 A CN 112981201A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
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Abstract
A magnesium-zinc-calcium alloy comprises magnesium, zinc and calcium, wherein the atomic percent of the magnesium is greater than that of the zinc, the atomic percent of the zinc is greater than that of the calcium, the mixing entropy range of the magnesium-zinc-calcium alloy is 0.6R to 1R, and R is an ideal gas constant. The invention also provides magnesium-zinc-calcium alloy powder, which comprises the magnesium-zinc-calcium alloy. The magnesium-zinc-calcium alloy has a low degradation rate through the mixing entropy range of 0.6R to 1R.
Description
Technical Field
The invention relates to a ternary alloy, in particular to a magnesium-zinc-calcium alloy and magnesium-zinc-calcium alloy powder.
Background
Modern medicine has been used to temporarily replace damaged organs, tissues or bones by implanting "biodegradable medical implants" within the body of an organism. As organs, tissues or bones regenerate and heal, biodegradable medical implants also gradually degrade in an attempt to minimize long-term effects on the organism.
The metal material is suitable for manufacturing biodegradable medical implants because of the properties of high mechanical strength, good elasticity, high plasticity and the like. However, the body fluid of the living body inevitably corrodes the metal material implanted in the body, and the corrosion of the metal material by the body fluid causes the gradual loss of the metal material implanted in the body, and then the biodegradable medical implant may lose its function before the organ, tissue or bone of the living body is not completely regenerated and healed. And the products produced by the corrosion of metallic materials by body fluids may also be harmful to living organisms. Therefore, for biodegradable medical implants, the biocompatibility, mechanical properties and corrosion resistance of metallic materials are important keys.
The magnesium alloy has biodegradability and is widely applied to be made into biodegradable medical implants, the degraded product of the magnesium alloy is metabolizable and nontoxic to organisms, and the only disadvantage is that the degradation rate of the magnesium alloy is difficult to control. In order to control the degradation rate of magnesium alloy, there is a technology of adding other elements such as tin element, aluminum element, rare earth element, etc. to magnesium alloy, but such elements may remain in the organism or cause adverse effects of metabolism accompanying the degradation of the alloy, and thus there is still a safety concern in clinical application. For example, Chinese patent application publication No. CN 108823476A relates to an Mg-Zn-Sn magnesium alloy, which controls the second phase component in the Mg-Zn-Sn magnesium alloy by adding Sn and matching with a smelting process, thereby achieving the purposes of improving the corrosion resistance and good degradation rate controllability of the Mg-Zn-Sn magnesium alloy.
In addition, surface treatment is also a technique commonly used for controlling the degradation rate of magnesium alloys, but corrosion resistance, adhesion, biocompatibility and the like are all considered, and the substrate is only a magnesium alloy, so that applicable corrosion-resistant coatings are also limited. For example, Chinese patent publication No. CN103418035B, the purpose of controlling the degradation speed of the blood vessel stent is achieved by forming a surface coating on the magnesium alloy blood vessel stent, wherein the surface coating comprises biodegradable high molecular material and additive particles, and the additive particles are Mg, MgO, Mg (OH)2One kind of (1).
Therefore, for the development of biodegradable medical implants, it is an urgent problem to control the degradation rate of metal materials and to reduce the degradation rate of metal materials.
Disclosure of Invention
A first object of the present invention is to provide a magnesium zinc calcium alloy that ameliorates at least one of the disadvantages of the prior art.
The magnesium-zinc-calcium alloy comprises magnesium, zinc and calcium, wherein the atomic percent of the magnesium is greater than that of the zinc, the atomic percent of the zinc is greater than that of the calcium, the mixing entropy range of the magnesium-zinc-calcium alloy is 0.6R-1R, and R is an ideal gas constant.
The magnesium-zinc-calcium alloy comprises, by taking the atomic percent of the magnesium-zinc-calcium alloy as 100 at%, 14 at% to 30 at% of zinc, 5 at% to 15 at% of calcium, and the balance of magnesium and inevitable impurities.
The magnesium-zinc-calcium alloy comprises, by weight, 100 wt% of the magnesium-zinc-calcium alloy, 30 at% to 50 wt% of zinc, 6 at% to 15 wt% of calcium, and the balance magnesium and inevitable impurities.
The mixed entropy of the magnesium-zinc-calcium alloy is calculated according to a formula I,
[ formula I]△S＝-R(XMglnXMg+XZnlnXZn+XCalnXCa)；
In formula I, R is an ideal gas constant, XMgIs the atomic molar ratio of magnesium, XZnIs the atomic molar ratio of zinc, XCaIs the atomic molar ratio of calcium, ln is the natural logarithm.
A second object of the present invention is to provide a magnesium zinc calcium alloy powder that can ameliorate at least one of the disadvantages of the prior art.
The magnesium-zinc-calcium alloy powder comprises the magnesium-zinc-calcium alloy and has the average particle diameter D50The range of (B) is 40 μm or less.
The invention has the beneficial effects that: the degradation rate of the magnesium-zinc-calcium alloy is controlled by controlling the mixing entropy of the magnesium-zinc-calcium alloy, and the magnesium-zinc-calcium alloy has a lower degradation rate by controlling the mixing entropy of the magnesium-zinc-calcium alloy to be 0.6R to 1R.
Detailed Description
The present invention will be described in detail below:
the magnesium-zinc-calcium alloy comprises magnesium, zinc and calcium, wherein the atomic percent of the magnesium is greater than that of the zinc, the atomic percent of the zinc is greater than that of the calcium, and the mixing entropy range of the magnesium-zinc-calcium alloy is 0.6R-1R.
Wherein, the mixed entropy of the magnesium-zinc-calcium alloy is calculated according to a formula I:
[ formula I]△S＝-R(XMglnXMg+XZnlnXZn+XCalnXCa)；
R is an ideal gas constant, XMgIs the atomic molar ratio of magnesium, XZnIs the atomic molar ratio of zinc, XCaIs the atomic molar ratio of calcium, ln is the natural logarithm.
According to formula I, in some embodiments of the magnesium-zinc-calcium alloy of the present invention, the atomic percent of zinc is in a range of 14 at% to 30 at%, the atomic percent of calcium is in a range of 5 at% to 15 at%, and the balance is magnesium and unavoidable impurities, based on 100 at% of the magnesium-zinc-calcium alloy, where the entropy of mixing of the magnesium-zinc-calcium alloy is in a range of 0.6R to 1R. If the weight percentage of the magnesium-zinc-calcium alloy is 100 wt%, the weight percentage of the zinc is 30 wt% to 50 wt%, the weight percentage of the calcium is 6 wt% to 15 wt%, and the balance is magnesium and inevitable impurities.
In some embodiments of the invention, the phase composition of the magnesium-zinc-calcium alloy comprises a Hexagonal Closest Packing (HCP) phase, Ca2Mg6Zn3Phase, and MgZn phase.
The magnesium-zinc-calcium alloy is in the form of powder, block, plate, wire, etc. The preparation method of the magnesium-zinc-calcium alloy is not particularly limited, and the existing process technology for manufacturing the alloy material can be flexibly selected according to the subsequent application of the magnesium-zinc-calcium alloy, such as but not limited to spray forming (spray forming), Vacuum Arc Remelting (VAR), casting (casting), continuously cast steel (continuous casting), extrusion forming (extrusion), forging (forming), or wire stretching.
In one embodiment of the present invention, the magnesium-zinc-calcium alloy is in the form of powder. The magnesium-zinc-calcium alloy powder comprises the magnesium-zinc-calcium alloy as described above, and the average particle diameter D of the magnesium-zinc-calcium alloy powder50The range of (B) is 40 μm or less.
Subsequent applications of the magnesium zinc calcium alloy, such as but not limited to biodegradable medical implants (specific classes of biodegradable medical implants such as but not limited to bone screws, bone plates, vascular stents, etc. In some embodiments of the invention, the magnesium zinc calcium alloy powder is formed into a biodegradable medical implant, for example, but not limited to, by metal injection molding.
The invention will be further described in the following examples, but it should be understood that the examples are illustrative only and should not be construed as limiting the practice of the invention.
Examples 1 to 3 and comparative example 1
In examples 1 to 3 and comparative example 1, a magnesium-zinc-calcium alloy was produced by a production method including the steps of:
step (1): according to the element content of the magnesium-zinc-calcium alloy to be prepared, preparing magnesium, zinc and calcium raw materials with required weight, and carrying out air spraying method by using an air spraying furnace to prepare magnesium-zinc-calcium alloy powder. The raw materials are placed in a crucible (the crucible temperature is 700 ℃) of the gas-jet furnace, the raw materials are melted into a molten liquid at the melting temperature, and then the molten liquid is sprayed by inert gas with the pressure of 3Mpa to form magnesium-zinc-calcium alloy powder.
Step (2): pressing the magnesium-zinc-calcium alloy powder into blocks with the diameter of 30mm and the height of 10mm by using the pressure of 250Mpa, and then sintering the blocks in vacuum at 350 ℃ for 2 hours to form the magnesium-zinc-calcium alloy block.
In examples 1 to 3 and comparative example 1, the melting temperature, the element content and the mixing entropy (. DELTA.S) of the magnesium-zinc-calcium alloy in step (1),and the average particle diameter (D) of the magnesium-zinc-calcium alloy powder50) As shown in table 1.
TABLE 1
[ Property evaluation ]
In examples 1 to 3 and comparative example 1, the degradation rates of the magnesium-zinc-calcium alloy powder and the magnesium-zinc-calcium alloy bulk material were measured by the following measurement methods, and the evaluation results are shown in table 2.
1. Degradation rate of magnesium-zinc-calcium alloy powder:
statically immersing 5 g of magnesium-zinc-calcium alloy powder in 2000 ml of 0.5 wt% saline solution, measuring the generation amount of hydrogen generated by degradation of the magnesium-zinc-calcium alloy powder in 10 minutes and the generation amount of hydrogen generated by degradation of the magnesium-zinc-calcium alloy powder in 30 minutes, and calculating the degradation rate of the magnesium-zinc-calcium alloy powder according to the following formula:
degradation rate (cc/g · min) — hydrogen generation amount (cc) ÷ [ weight (g) × time (min) of the magnesium-zinc-calcium alloy powder ].
2. Degradation rate of magnesium-zinc-calcium alloy block
The area is 24cm2The magnesium-zinc-calcium alloy block material is statically soaked in 2000 ml of 0.5 wt% of salt solution, the generation amount of hydrogen generated by degradation of the magnesium-zinc-calcium alloy block material after being statically soaked for 1 hour is measured, and the degradation rate of the magnesium-zinc-calcium alloy block material is calculated according to the following formula:
degradation Rate (cc/cm)2Hr) — hydrogen generation amount (cc) ÷ [ area of magnesium zinc calcium alloy block material (cm))2) X time (hr)]。
TABLE 2
As can be seen from table 2, the entropy of mixing of the mg-zn-ca alloys of examples 1 to 3 is 0.65R to 0.81R, and the mg-zn-ca alloys have slower degradation rate in both powder and bulk forms, which proves that the mg-zn-ca alloys can have lower degradation rate by making the entropy of mixing of the mg-zn-ca alloys be in the range of 0.6R to 1R.
However, in comparative example 1, the entropy of the mixture of the magnesium-zinc-calcium alloy is 0.53R, which results in a faster degradation rate of the magnesium-zinc-calcium alloy.
In summary, the magnesium-zinc-calcium alloy of the present invention can control the degradation rate of the magnesium-zinc-calcium alloy only by controlling the entropy of the magnesium-zinc-calcium alloy, and the entropy range of the magnesium-zinc-calcium alloy is 0.6R to 1R, so that the magnesium-zinc-calcium alloy has a lower degradation rate. The magnesium-zinc-calcium alloy is suitable for serving as a biodegradable medical implant in subsequent application, and the magnesium-zinc-calcium alloy comprises the following components of magnesium, zinc and calcium which are all elements capable of being metabolized by organisms, so that the doubt of element residue in the organisms is avoided. In addition, the magnesium-zinc-calcium alloy powder has low activity, and can be suitable for being made into a biodegradable medical implant with a special shape by an additive manufacturing (additive manufacturing) technology. Therefore, the object of the present invention can be achieved.
However, the above description is only an example of the present invention, and the scope of the present invention should not be limited thereby, and all simple equivalent changes and modifications made according to the claims and the contents of the specification of the present invention are included in the scope of the present invention.
Claims (5)
1. The magnesium-zinc-calcium alloy is characterized in that: which comprises the following steps:
magnesium;
zinc; and
calcium;
wherein the atomic percent of magnesium is greater than the atomic percent of zinc, and the atomic percent of zinc is greater than the atomic percent of calcium;
the mixing entropy range of the magnesium-zinc-calcium alloy is 0.6R to 1R, and R is an ideal gas constant.
2. The magnesium-zinc-calcium alloy according to claim 1, wherein the atomic percent of zinc is in the range of 14 at% to 30 at%, the atomic percent of calcium is in the range of 5 at% to 15 at%, and the balance is magnesium and unavoidable impurities, based on the atomic percent of the magnesium-zinc-calcium alloy being 100 at%.
3. The magnesium-zinc-calcium alloy according to claim 1, wherein the weight percentage of zinc is in the range of 30 wt% to 50 wt%, the weight percentage of calcium is in the range of 6 wt% to 15 wt%, and the balance is magnesium and unavoidable impurities, based on 100 wt% of the magnesium-zinc-calcium alloy.
4. The Mg-Zn-Ca alloy according to claim 1, wherein the entropy of mixing of the Mg-Zn-Ca alloy is calculated according to formula I,
[ formula I]△S＝-R(XMglnXMg+XZnlnXZn+XCalnXCa)；
In formula I, R is an ideal gas constant, XMgIs the atomic molar ratio of magnesium, XZnIs the atomic molar ratio of zinc, XCaIs the atomic molar ratio of calcium, ln is the natural logarithm.
5. A magnesium-zinc-calcium alloy powder is characterized in that: which comprises the following steps:
the magnesium-zinc-calcium alloy according to claim 1, wherein the magnesium-zinc-calcium alloy powder has an average particle diameter D50The range of (B) is 40 μm or less.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023232158A1 (en) * | 2022-11-24 | 2023-12-07 | 常州大学 | Medical degradable znmgca medium-entropy alloy, and preparation method therefor and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030000608A1 (en) * | 1996-11-01 | 2003-01-02 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Magnesium alloy and heat treatment method thereof |
| CN106854724A (en) * | 2016-12-29 | 2017-06-16 | 赵建武 | A kind of medical magnesium alloy materials containing rare earth element and preparation method thereof |
| CN109161766A (en) * | 2018-09-21 | 2019-01-08 | 湘潭大学 | A kind of Biological magnesium alloy and preparation method thereof of the layer of consolidation containing amorphous |
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- 2019-12-17 CN CN201911297867.7A patent/CN112981201A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030000608A1 (en) * | 1996-11-01 | 2003-01-02 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Magnesium alloy and heat treatment method thereof |
| CN106854724A (en) * | 2016-12-29 | 2017-06-16 | 赵建武 | A kind of medical magnesium alloy materials containing rare earth element and preparation method thereof |
| CN109161766A (en) * | 2018-09-21 | 2019-01-08 | 湘潭大学 | A kind of Biological magnesium alloy and preparation method thereof of the layer of consolidation containing amorphous |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023232158A1 (en) * | 2022-11-24 | 2023-12-07 | 常州大学 | Medical degradable znmgca medium-entropy alloy, and preparation method therefor and use thereof |
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