CN113684407A - A kind of degradable Mg-Zn-Sr-Ag magnesium alloy and its preparation method and application - Google Patents
A kind of degradable Mg-Zn-Sr-Ag magnesium alloy and its preparation method and application Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 96
- 229910003800 Sr-Ag Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 35
- 239000000956 alloy Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 30
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- 239000011701 zinc Substances 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 7
- 229910017706 MgZn Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 abstract description 19
- 230000007797 corrosion Effects 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 239000007943 implant Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000005275 alloying Methods 0.000 abstract 1
- 238000001727 in vivo Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000001356 surgical procedure Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000012890 simulated body fluid Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 231100001083 no cytotoxicity Toxicity 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000011164 ossification Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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Abstract
本发明涉及生物医用金属植入材料技术领域，尤其涉及一种可降解Mg‑Zn‑Sr‑Ag系镁合金及其制备方法与应用。所述可降解Mg‑Zn‑Sr‑Ag系镁合金按质量百分比计，包括以下元素：Zn3.4～4.3％，Sr0.2～0.5％，Ag0.2～1.0％和余量的Mg；本发明的Mg‑Zn‑Sr‑Ag系镁合金，通过对添加合金元素的调控，可以获得在体内良好的力学性能和降解速率，所述可降解Mg‑Zn‑Sr‑Ag系镁合金具有较高的生物安全性、良好的强韧性和较好的耐腐蚀性，可以很好的避免应力遮挡效应以及减少二次手术的痛苦。
The invention relates to the technical field of biomedical metal implant materials, in particular to a degradable Mg-Zn-Sr-Ag magnesium alloy and a preparation method and application thereof. The degradable Mg-Zn-Sr-Ag magnesium alloy includes the following elements by mass percentage: Zn 3.4-4.3%, Sr 0.2-0.5%, Ag 0.2-1.0% and the balance of Mg; The invented Mg-Zn-Sr-Ag-based magnesium alloy can obtain good mechanical properties and degradation rate in vivo by regulating the addition of alloying elements, and the degradable Mg-Zn-Sr-Ag-based magnesium alloy has higher It has good biological safety, good toughness and good corrosion resistance, which can well avoid the stress shielding effect and reduce the pain of secondary surgery.
Description
Technical Field
The invention relates to the technical field of biomedical metal implant materials, in particular to a degradable Mg-Zn-Sr-Ag magnesium alloy and a preparation method and application thereof.
Background
At present, the medical metal materials widely applied to clinical use mainly comprise 316 stainless steel, cobalt-chromium alloy, titanium alloy and the like, and the metal materials play an important role in medical clinical application. But their elastic modulus is much different from that of human bone, and stress shielding effect is easily generated. Stainless steel releases toxic metal ions due to corrosion, and phenomena of allergy and poisoning can occur. Although the titanium alloy has good corrosion resistance, the titanium alloy can not be degraded, thereby bringing the pain of secondary operation and improving the cost. The magnesium and the magnesium alloy have high specific strength, high specific rigidity and good biocompatibility, and the density and the elastic modulus of the magnesium alloy are close to those of human bones, so that the stress shielding effect can be well avoided. Magnesium is also a macroelement in human bodies, and cannot generate side effects on human bodies and pain of secondary operations in the natural corrosion and degradation process.
However, how to make magnesium alloy have higher biological safety, good toughness and better corrosion resistance at the same time is still an unsolved problem.
Disclosure of Invention
The invention aims to provide a degradable Mg-Zn-Sr-Ag magnesium alloy and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a degradable Mg-Zn-Sr-Ag magnesium alloy, which comprises the following elements in percentage by mass: 3.4-4.3% of Zn, 0.2-0.5% of Sr0.2-1.0% of Ag and the balance of Mg.
Preferably, the degradable Mg-Zn-Sr-Ag magnesium alloy comprises the following components in phase composition: MgZn phase, Mg17Sr2Phase and Mg4An Ag phase.
The invention provides a preparation method of the degradable Mg-Zn-Sr-Ag magnesium alloy, which comprises the following steps:
according to the mass ratio of the degradable Mg-Zn-Sr-Ag magnesium alloy elements, metal magnesium, metal silver, metal zinc and an Mg-Sr intermediate alloy are sequentially smelted and cast to obtain the degradable Mg-Zn-Sr-Ag magnesium alloy.
Preferably, the smelting comprises: melting magnesium metal in an environment with the temperature of 760-800 ℃, then adding silver metal to melt, cooling to 720 ℃, adding an Mg-Sr intermediate alloy, and adding zinc metal to melt after the Mg-Sr intermediate alloy is melted; the smelting is carried out under a protective atmosphere.
Preferably, the Mg-Sr intermediate alloy comprises 20-25% of Sr and the balance of Mg in percentage by mass.
Preferably, the gas providing the protective atmosphere comprises SF6And N2。
Preferably, SF in said protective atmosphere6And N2Is 2: 98.
Preferably, the temperature of the alloy liquid is 700-740 ℃ during the pouring.
Preferably, the preheating temperature of the casting mold for casting is 260-320 ℃.
The invention provides application of the degradable Mg-Zn-Sr-Ag magnesium alloy in the scheme or the degradable Mg-Zn-Sr-Ag magnesium alloy prepared by the preparation method in preparation of biomedical metal materials.
The invention provides a degradable Mg-Zn-Sr-Ag magnesium alloy, which comprises the following elements in percentage by mass: 3.4-4.3% of Zn, 0.2-0.5% of Sr, 0.2-1.0% of Ag and the balance of Mg.
Zn in the degradable Mg-Zn-Sr-Ag magnesium alloy has the solid solution strengthening effect on the magnesium alloy, and meanwhile, the occurrence of non-basal plane slippage of the magnesium alloy at room temperature is effectively promoted, and the plastic processing capacity of the magnesium alloy is improved; the Zn is used as a trace element necessary for a human body, has no cytotoxicity and good biocompatibility, and the content of the Zn is controlled in the range, so that the Mg-Zn-Sr-Ag magnesium alloy is beneficial to having good strength and corrosion resistance. Sr is an important constituent element of human bones, has no cytotoxicity and can promote bone formation, and the content of Sr is controlled in the range, so that the degradable Mg-Zn-Sr-Ag magnesium alloy has high biological safety, good toughness and good corrosion resistance. The Ag has the nonspecific broad-spectrum antibacterial effect, and the magnesium alloy can be ensured to have good mechanical property and corrosion resistance by controlling the content of the Ag within the range.
In conclusion, the degradable Mg-Zn-Sr-Ag magnesium alloy has higher biological safety, good toughness and better corrosion resistance by controlling the types and contents of all elements.
The invention also provides a preparation method of the Mg-Zn-Sr-Ag magnesium alloy in the technical scheme, and the preparation method is simple and easy to operate.
Drawings
FIG. 1 is a microstructure diagram of a Mg-Zn-Sr-Ag-based magnesium alloy produced in example 1;
FIG. 2 is a microstructure diagram of a Mg-Zn-Sr-Ag-based magnesium alloy produced in example 2;
FIG. 3 is a microstructure diagram of a Mg-Zn-Sr-Ag-based magnesium alloy produced in example 3;
FIG. 4 is a microstructure diagram of the Mg-Zn-Sr-Ag based magnesium alloy prepared in comparative example 1;
FIG. 5 is a microstructure diagram of the Mg-Zn-Sr-Ag based magnesium alloy prepared in comparative example 2;
FIG. 6 is a microstructure of the Mg-Zn-Sr-Ag based magnesium alloy prepared in comparative example 3.
Detailed Description
The invention provides an Mg-Zn-Sr-Ag magnesium alloy which comprises the following elements in percentage by mass: 3.4-4.3% of Zn, 0.2-0.5% of Sr, 0.2-1.0% of Ag and the balance of Mg.
The Mg-Zn-Sr-Ag magnesium alloy comprises 3.4-4.3% of Zn by mass, preferably 3.6-4.1% of Zn by mass, and more preferably 4.0% of Zn by mass. In the invention, Zn in the Mg-Zn-Sr-Ag magnesium alloy has the solid solution strengthening effect on the magnesium alloy, and simultaneously, the occurrence of non-basal plane slippage of the magnesium alloy at room temperature is effectively promoted, and the plastic processing capacity of the magnesium alloy is improved; zn is used as a necessary trace element for human bodies, has no cytotoxicity and has good biocompatibility. The invention controls the Zn content in the range, can ensure that the Mg-Zn-Sr-Ag magnesium alloy has better strength and corrosion resistance;
the Mg-Zn-Sr-Ag magnesium alloy comprises 0.2-0.5% of Sr, preferably 0.3-0.5%, and more preferably 0.5% by mass. In the present invention, Sr is an important constituent element of human bone, has no cytotoxicity, and can promote bone formation. When the Sr content is too high, a large amount of second phase is formed in the grain boundary, and the corrosion resistance of the alloy is lowered. The invention controls the Sr content in the range, thereby ensuring that the Mg-Zn-Sr-Ag magnesium alloy has higher biological safety, good toughness and better corrosion resistance.
The Mg-Zn-Sr-Ag magnesium alloy comprises 0.2-1.0% of Ag, preferably 0.2-0.5%, and more preferably 0.5% by mass. In the invention, silver is one of trace elements in human tissues, the trace silver is harmless to human bodies, the Ag element can adsorb bacterial protease, the enzyme with the respiration function can lose the effect, and bacteria can die. The invention can ensure that the Mg-Zn-Sr-Ag magnesium alloy has good mechanical property and corrosion resistance by controlling the Ag content in the range.
The Mg-Zn-Sr-Ag magnesium alloy comprises the balance of Mg.
In terms of phase composition, the degradable Mg-Zn-Sr-Ag magnesium alloy preferably comprises: MgZn phase, Mg17Sr2Phase and Mg4An Ag phase. In the present invention, the MgZn phase is dotted, and the Mg phase is17Sr2The phase is strip-shaped and is uniformly distributed in the matrix, and the Mg4The Ag phase is short and coarse and has the function of refining grains, the MgZn phase and the Mg phase17Sr2Phase and Mg4The Ag phase can improve the strength of the alloy.
In the invention, the average grain size of the degradable Mg-Zn-Sr-Ag magnesium alloy is preferably 80-110 μm.
The invention provides a preparation method of the degradable Mg-Zn-Sr-Ag magnesium alloy, which comprises the following steps:
according to the mass ratio of the degradable Mg-Zn-Sr-Ag magnesium alloy elements, metal magnesium, metal silver, metal zinc and an Mg-Sr intermediate alloy are sequentially smelted and cast to obtain the degradable Mg-Zn-Sr-Ag magnesium alloy.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In the present invention, the metallic magnesium is preferably a magnesium ingot having a purity of 99.94 wt%; the metal silver is preferably silver wire with the purity of 99.99 wt%, and the metal zinc is preferably zinc ingot with the purity of 99.995 wt%; the Mg-Sr intermediate alloy preferably comprises 20-25% of Sr and the balance of Mg in percentage by mass, and the mass percentage of Sr in the Mg-Sr intermediate alloy is more preferably 20%.
In the invention, the amounts of the metal zinc, the metal silver, the Mg-Sr intermediate alloy and the metal magnesium are calculated by referring to the element composition of the Mg-Zn-Sr-Ag magnesium alloy in the technical scheme.
In the present invention, the smelting preferably includes: melting magnesium metal in an environment with the temperature of 760-800 ℃, then adding metal silver until the metal silver is melted, cooling to 720 ℃, adding an Mg-Sr intermediate alloy, and adding metal zinc until the Mg-Sr intermediate alloy is melted. The present invention more preferably melts magnesium metal in an environment of 780 ℃.
In the present invention, the smelting is preferably carried out under a protective atmosphere; the gas providing said protective atmosphere preferably comprises SF6And N2. Invention for said SF6And N2Is prepared byAny particular limitation may be imposed by the use of a compounding ratio known to those skilled in the art. In a specific embodiment of the invention, the SF6And N2Is 2: 98. According to the invention, the protective gas is preferably introduced when the temperature of the furnace rises to 600 ℃.
After the smelting is finished, the obtained alloy liquid is poured. In the invention, the temperature of the alloy liquid is preferably 700-740 ℃, and more preferably 710-720 ℃ when the pouring is carried out; the preheating temperature of a casting mold for casting is preferably 260-320 ℃, and more preferably 280-300 ℃; the casting mould is preferably a ceramic mould; the atmosphere of the casting is preferably SF6And N2The mixed atmosphere of (3); the invention is suitable for the SF in the mixed atmosphere6And N2The compounding ratio of (A) is not particularly limited, and those known to those skilled in the art may be used. In a specific embodiment of the invention, the mixed atmosphere is SF6And N2Is 2: 98.
In the present invention, the purpose of preheating the casting mold is to avoid the problems of composition segregation and non-uniform structure caused by rapid solidification of the alloy liquid.
The invention also provides the application of the Mg-Zn-Sr-Ag magnesium alloy in the technical scheme or the Mg-Zn-Sr-Ag magnesium alloy prepared by the preparation method in the technical scheme in preparation of biomedical metal materials. The method of the present invention is not particularly limited, and the method may be performed by a method known to those skilled in the art.
The following will explain the degradable Mg-Zn-Sr-Ag magnesium alloy and the preparation method and application thereof in detail with reference to the examples, but they should not be construed as limiting the scope of the invention.
Example 1
The degradable Mg-Zn-Sr-Ag magnesium alloy comprises the following components: 3.97% of Zn, 0.43% of Sr, 0.2% of Ag and the balance of Mg;
the adopted raw materials are as follows: a magnesium ingot with the purity of 99.94 wt%, a zinc ingot with the purity of 99.995 wt%, a silver wire with the purity of 99.99 wt% and an Mg-Sr intermediate alloy containing 20 mass percent of Sr;
the preparation process comprises the following steps: 926.16g of magnesium ingot is added into a resistance furnace, the temperature is set to 780 ℃, SF with the volume ratio of 2:98 is introduced when the temperature of the furnace is raised to 600 DEG C6And N2After the magnesium ingot is melted, 2.04g of silver wire is added, the mixture is stirred for 2min, after the temperature is reduced to 720 ℃, 20.4g of Mg-Sr intermediate alloy is added for melting, the mixture is stirred for 4min, 40.8g of zinc ingot is added, the mixture is stirred for 5min after being melted, the mixture is kept stand for 30min, and finally the mixture is poured into a ceramic mold at the temperature of 720 ℃.
FIG. 1 is a microstructure of an Mg-Zn-Sr-Ag magnesium alloy according to example 1, in which the average grain size of the Mg-Zn-Sr-Ag magnesium alloy is 102.63 μm, as can be seen from FIG. 1;
according to the requirements of GB/T228.1-2010, the Mg-Zn-Sr-Ag magnesium alloy in the example 1 is tested for yield strength, tensile strength and elongation; the results show that: the magnesium alloy of example 1 has yield strength and tensile strength of 97MPa and 173MPa, respectively, and elongation of 11.58%;
the corrosion rate was 0.7058 mm/year for 8 days in Hank's simulated body fluid as required by ASTM G31-72.
Example 2
The degradable Mg-Zn-Sr-Ag magnesium alloy comprises the following components: 3.97% of Zn, 0.43% of Sr, 0.5% of Ag and the balance of Mg;
the adopted raw materials are as follows: a magnesium ingot with the purity of 99.94 wt%, a zinc ingot with the purity of 99.995 wt%, a silver wire with the purity of 99.99 wt% and an Mg-Sr intermediate alloy containing 20 mass percent of Sr;
the preparation process comprises the following steps: 923.1g of magnesium ingot is added into a resistance furnace, the temperature is set to 780 ℃, SF with the volume ratio of 2:98 is introduced when the temperature of the furnace is raised to 600 DEG C6And N2After the magnesium ingot is melted, 5.1g of silver wire is added, the mixture is stirred for 2min, 25.5g of Mg-Sr intermediate alloy is added for melting, the mixture is stirred for 4min, the temperature is reduced to 720 ℃, 40.8g of zinc ingot is added, the mixture is stirred for 5min after melting, the mixture is kept stand for 30min, and finally the mixture is poured into a ceramic mold at the temperature of 720 ℃.
FIG. 2 is a microstructure of the Mg-Zn-Sr-Ag magnesium alloy of example 2, and it is understood from FIG. 2 that the Mg-Zn-Sr-Ag magnesium alloy has an average crystal grain size of 83.28. mu.m;
according to the requirements of GB/T228.1-2010, the Mg-Zn-Sr-Ag magnesium alloy in the example 2 is tested for yield strength, tensile strength and elongation; the results show that: the yield strength and the tensile strength of the magnesium alloy in the embodiment 2 are 102MPa and 182MPa respectively, and the elongation is 12.20 percent;
the corrosion rate was 0.5431 mm/year for 8 days as tested in Hank's simulated body fluid according to ASTM G31-72.
Example 3
The degradable Mg-Zn-Sr-Ag magnesium alloy comprises the following components: 3.97% of Zn, 0.43% of Sr, 1.0% of Ag and the balance of Mg;
the adopted raw materials are as follows: a magnesium ingot with the purity of 99.94 wt%, a zinc ingot with the purity of 99.995 wt%, a silver wire with the purity of 99.99 wt% and an Mg-Sr intermediate alloy containing 20 mass percent of Sr;
the preparation process comprises the following steps: 918g of magnesium ingot is added into a resistance furnace, the temperature is set to be 780 ℃, SF with the volume ratio of 2:98 is introduced when the temperature of the furnace is increased to 600 DEG C6And N2After the magnesium ingot is melted, 10.2g of silver wire is added, the mixture is stirred for 2min, 25.5g of Mg-Sr intermediate alloy is added for melting, the mixture is stirred for 4min, the temperature is reduced to 720 ℃, 40.8g of zinc ingot is added, the mixture is stirred for 5min after melting, the mixture is kept stand for 30min, and finally the mixture is poured into a ceramic mold at the temperature of 720 ℃.
FIG. 3 is a microstructure of an Mg-Zn-Sr-Ag magnesium alloy according to example 3, in which the average grain size of the Mg-Zn-Sr-Ag magnesium alloy is 102.63 μm, as is clear from FIG. 3;
according to the requirements of GB/T228.1-2010, the Mg-Zn-Sr-Ag magnesium alloy in the example 3 is tested for yield strength, tensile strength and elongation; the results show that: the yield strength and the tensile strength of the magnesium alloy in the embodiment 3 are 85MPa and 175MPa respectively, and the elongation is 11.65%;
the corrosion rate was 0.7287 mm/year for 8 days in Hank's simulated body fluid as required by ASTM G31-72.
Comparative example 1
Preparation of silver-free Mg-Zn-Sr magnesium alloy
Composition of the magnesium alloy: 3.98 percent of Zn, 0.49 percent of Sr and the balance of Mg;
the adopted raw materials are as follows: a magnesium ingot with the purity of 99.94 wt%, a zinc ingot with the purity of 99.995 wt% and an Mg-Sr intermediate alloy containing 20 mass percent of Sr;
the preparation process comprises the following steps: 928.2g of magnesium ingot is added into a resistance furnace, the temperature is set to 780 ℃, SF with the volume ratio of 2:98 is introduced when the temperature of the furnace is raised to 600 DEG C6And N2After the magnesium ingot is melted, cooling to 720 ℃, adding 25.5g of Mg-Sr intermediate alloy for melting, stirring for 4min, adding 40.8g of zinc ingot, stirring for 5min after melting, standing for 30min, and finally pouring into a ceramic mold at the temperature of 720 ℃.
FIG. 4 is a microstructure of the Mg-Zn-Sr-Ag based magnesium alloy according to comparative example 1, and it is understood from FIG. 4 that the average crystal grain size of the magnesium alloy according to comparative example 1 is 102.63 μm;
according to the GB/T228.1-2010 requirement, the magnesium alloy of comparative example 1 is tested for yield strength, tensile strength and elongation; the results show that: comparative example 1 the magnesium alloy had yield strength and tensile strength of 82MPa and 161MPa, respectively, and elongation of 10.30%;
the corrosion rate was 0.7631 mm/year for 8 days in Hank's simulated body fluid as required by ASTM G31-72.
Comparative example 2
Preparing Mg-Zn-Sr-Ag magnesium alloy with excessive silver content
The degradable medical alloy comprises the following components: 3.98% of Zn, 0.49% of Sr, 2.0% of Ag and the balance of Mg;
the adopted raw materials are as follows: a magnesium ingot with the purity of 99.94 wt%, a zinc ingot with the purity of 99.995 wt%, a silver wire with the purity of 99.99 wt% and an Mg-Sr intermediate alloy containing 20 mass percent of Sr;
the preparation process comprises the following steps: 907.8g of magnesium ingot is added into a resistance furnace, the temperature is set to 780 ℃, SF with the volume ratio of 2:98 is introduced when the temperature of the furnace is raised to 600 DEG C6And N2After the magnesium ingot is melted, 20.4g of silver wire is added, the mixture is stirred for 2min, 25.5g of Mg-Sr intermediate alloy is added for melting, the mixture is stirred for 4min, the temperature is reduced to 720 ℃, 40.8g of zinc ingot is added, the mixture is stirred for 5min after melting, the mixture is kept stand for 30min, and finally the mixture is poured into a ceramic mold at the temperature of 720 ℃.
FIG. 5 is a microstructure of the Mg-Zn-Sr-Ag magnesium alloy according to comparative example 2, and it is understood from FIG. 5 that the Mg-Zn-Sr-Ag magnesium alloy has an average crystal grain size of 110.43 μm;
according to the GB/T228.1-2010 requirement, the Mg-Zn-Sr-Ag series magnesium alloy of the comparative example 2 is tested for yield strength, tensile strength and elongation; the results show that: comparative example 2 the magnesium alloy had yield strength and tensile strength of 81MPa and 142MPa, respectively, and elongation of 6.67%;
the corrosion rate was 0.9773 mm/year for 8 days in Hank's simulated body fluid as required by ASTM G31-72.
Comparative example 3
Preparing Mg-Zn-Sr-Ag magnesium alloy with excessive strontium content
The degradable medical alloy comprises the following components: 3.98% of Zn, 1.0% of Sr, 0.5% of Ag and the balance of Mg;
the adopted raw materials are as follows: a magnesium ingot with the purity of 99.94 wt%, a zinc ingot with the purity of 99.995 wt%, a silver wire with the purity of 99.99 wt% and an Mg-Sr intermediate alloy containing 20 mass percent of Sr;
the preparation process comprises the following steps: 948.6g of magnesium ingot is added into a resistance furnace, the temperature is set to 780 ℃, SF with the volume ratio of 2:98 is introduced when the temperature of the furnace is raised to 600 DEG C6And N2After the magnesium ingot is melted, 5.1g of silver wire is added, the mixture is stirred for 2min, 25.5g of Mg-Sr intermediate alloy is added for melting, the mixture is stirred for 4min, the temperature is reduced to 720 ℃, 40.8g of zinc ingot is added, the mixture is stirred for 5min after melting, the mixture is kept stand for 30min, and finally the mixture is poured into a ceramic mold at the temperature of 720 ℃.
FIG. 6 is a microstructure of the Mg-Zn-Sr-Ag magnesium alloy according to comparative example 3, and it is understood from FIG. 6 that the Mg-Zn-Sr-Ag magnesium alloy has an average crystal grain size of 121.17 μm;
according to the GB/T228.1-2010 requirement, the Mg-Zn-Sr-Ag series magnesium alloy in the comparative example 3 is tested for yield strength, tensile strength and elongation; the results show that: comparative example 3 the yield strength and tensile strength of the magnesium alloy were 72MPa and 128MPa, respectively, and the elongation was 5.89%;
the corrosion rate was 1.2014 mm/year for 8 days in Hank's simulated body fluid as required by ASTM G31-72.
As can be seen from the above examples and comparative examples, the magnesium alloy obtained by controlling the elemental composition and content of the magnesium alloy in the invention has high biological safety, good toughness and good degradation controllability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
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