CN113122761A - Degradable, tough and strong magnesium alloy and preparation method and application thereof - Google Patents
Degradable, tough and strong magnesium alloy and preparation method and application thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 223
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000011777 magnesium Substances 0.000 claims abstract description 16
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 15
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims description 84
- 238000004321 preservation Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 11
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000002792 vascular Effects 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910001278 Sr alloy Inorganic materials 0.000 claims description 2
- 229910000946 Y alloy Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 210000005036 nerve Anatomy 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 22
- 239000004033 plastic Substances 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 230000000399 orthopedic effect Effects 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000002513 implantation Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 7
- 210000000988 bone and bone Anatomy 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 239000007943 implant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035876 healing Effects 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 2
- 206010017076 Fracture Diseases 0.000 description 2
- 208000001132 Osteoporosis Diseases 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000002591 computed tomography Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 238000002595 magnetic resonance imaging Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 208000006735 Periostitis Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- -1 calcium-phosphorus compound Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 230000009818 osteogenic differentiation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 210000003460 periosteum Anatomy 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 210000000130 stem cell Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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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
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
-
- 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
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C23/00—Extruding metal; Impact extrusion
- B21C23/02—Making uncoated products
- B21C23/04—Making uncoated products by direct extrusion
- B21C23/08—Making wire, bars, tubes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Extrusion Of Metal (AREA)
Abstract
The invention belongs to the field of alloy materials, and discloses a degradable, high-toughness magnesium alloy, and a preparation method and application thereof. The magnesium alloy comprises Mg and also comprises the following components in percentage by mass: y0.4-8.0%, Sr 0.1-6.0%; the magnesium alloy further comprises Zn and/or Zr. The invention also provides a method for preparing a magnesium alloy bar by using the magnesium alloy. The magnesium alloy contains Y and Sr, which is beneficial to reducing the process conditions of the magnesium alloy in the plastic processing process, such as temperature, pressure and the like, not only can the plastic processing of the magnesium alloy become easy to operate, but also the mechanical properties of various shapes of instruments obtained after the plastic processing are obviously improved, and the application of the magnesium alloy in the medical field is facilitated; the tensile strength of the prepared magnesium alloy bar can reach 356MPa, the yield strength can reach 243MPa, the requirements of orthopedic implantation instruments on mechanical properties are met, and the magnesium alloy bar has good degradation performance.
Description
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a degradable, high-toughness magnesium alloy, and a preparation method and application thereof.
Background
Currently, the clinically used orthopedic implant apparatus is mainly made of traditional inert metal materials such as stainless steel, titanium-based alloy and cobalt-based alloy, and the like, and the inert metal materials have good mechanical strength and processability, but are not degradable after being implanted into a body, and can generate problems such as mechanical friction damage, toxic ion release, local inflammatory reaction and the like in the long-term service process. Because the elastic modulus of the inert metal material is greatly different from that of human bone tissue, the inert metal material generates obvious stress shielding effect after being implanted into human body, seriously influences the healing of the bone tissue, possibly causes osteoporosis and even causes the risk of secondary fracture. Moreover, the implantation device made of the inert metal material needs to be taken out through a secondary operation after the bone tissue is healed, so that the physiological pain and the economic burden of a patient are increased.
In view of the above, researchers developed magnesium alloy materials for medical use, and have the following significant advantages: (1) good biocompatibility. Magnesium ions released by the magnesium alloy in the degradation process not only can supplement magnesium element for the normal physiological function of a human body, but also can accelerate the formation of bone cells and the healing of bone tissues. (2) Good biomechanical compatibility. The density and the elastic modulus of the magnesium alloy are most similar to those of human bone tissues, so that the stress shielding effect and the osteoporosis caused by the stress shielding effect can be effectively avoided, and sufficient mechanical support can be provided for a diseased part. (3) Good biodegradability. The magnesium alloy is easy to corrode and degrade in the internal environment containing chloride ions, and the degradation product can be completely absorbed by the human body, so that the physiological pain and the economic burden of a patient caused by taking out the magnesium alloy in a secondary operation are avoided. (4) Good osteoblast inducibility. Magnesium ions released by the magnesium alloy in the degradation process can effectively induce osteogenic differentiation and proliferation of stem cells in periosteum, can accelerate healing of fracture parts, and is an ideal bone tissue repair material. (5) Good medical image visibility. After the magnesium alloy is completely degraded, a calcium-phosphorus compound can be formed at a corresponding part, and can be identified by image means such as MRI (magnetic resonance imaging) and CT (computed tomography), so that clinical follow-up noninvasive examination is conveniently carried out.
However, in the prior art, since plastic processing of magnesium alloy metal needs to be realized under extremely strict process conditions, the production and processing of magnesium alloy rods for preparing orthopedic implant instruments face a lot of technical problems, the quality of the magnesium alloy rods is seriously affected, and particularly, the mechanical properties of the prepared magnesium alloy rods are poor, so that a new magnesium alloy needs to be developed, the magnesium alloy is easy to perform plastic processing, the magnesium alloy rods for orthopedic implant instruments can be better prepared, and the magnesium alloy rods have good mechanical properties.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a degradable, tough magnesium alloy. Compared with the prior art, the process of processing the magnesium alloy into the magnesium alloy rod is easier, and the prepared magnesium alloy rod has good mechanical property and is very suitable for application in the medical field.
The invention provides a degradable, tough magnesium alloy in a first aspect.
Specifically, the invention provides a degradable, tough magnesium alloy, which comprises Mg and the following components in percentage by mass:
Y 0.4-8.0％
Sr 0.1-6.0％。
the magnesium alloy contains Y and Sr, which is beneficial to reducing the process conditions (temperature, pressure and the like) of the magnesium alloy in the plastic processing process, not only can the plastic processing of the magnesium alloy become easy to operate, but also the mechanical properties of instruments with various shapes obtained after the plastic processing are obviously improved.
Preferably, the magnesium alloy comprises the following components in percentage by mass:
Y 0.5-6.0％
Sr 0.1-5.0％。
preferably, the magnesium alloy further contains Zn and/or Zr. The inclusion of Zn and/or Zr in the magnesium alloy is advantageous for further improving the mechanical properties of various shaped articles made of the magnesium alloy.
Preferably, the magnesium alloy has 0.1 to 6.0 percent of Zn by mass; more preferably, the magnesium alloy has 0.1 to 5.0% Zn by mass.
Preferably, the magnesium alloy has Zr of 0.1 to 5.0 percent in mass fraction; more preferably, the magnesium alloy contains 0.1 to 4.0% by mass of Zr.
Further preferably, the magnesium alloy comprises the following components in percentage by mass:
preferably, the magnesium alloy contains, in addition to Mg, Y, Sr, Zn, Zr, the total amount of other elements is < 0.05% (mass fraction). According to the invention, through strictly controlling the contents of other elements, such as impurities of Fe, Cu, Ni and the like, the bar obtained after the magnesium alloy is finally subjected to plastic processing has better comprehensive mechanical properties and biodegradability.
The second aspect of the invention provides a preparation method of degradable, tough magnesium alloy.
Specifically, the invention provides a preparation method of a degradable, tough magnesium alloy, which comprises the following steps:
(1) mixing Mg, Y and Sr in a protective gas atmosphere, heating to melt, then heating, and standing to obtain a magnesium alloy melt;
(2) and (2) stirring the magnesium alloy melt prepared in the step (1), removing scum on the surface of the magnesium alloy melt, cooling, pouring into a mold, and cooling to prepare the magnesium alloy.
Preferably, in step (1), the protective gas is tetrafluoroethane. Under the high-temperature environment, tetrafluoroethane gas reacts with magnesium alloy melt to generate MgF with higher density2And the amorphous carbon and the two substances can be filled in a gap between the magnesium alloy melt and the oxide film very effectively, so that the tightness of the oxide film on the surface of the magnesium alloy melt is improved, and the diffusion movement of magnesium ions penetrating through the oxide film can be inhibited strongly, so that the generation of an oxidation reaction of the magnesium alloy melt is inhibited.
Preferably, in step (1), Y is added in the form of an Mg-Y alloy.
Preferably, in step (1), Sr is added in the form of a Mg-Sr alloy.
Preferably, in the step (1), Zn and/or Zr is/are also added during the mixing of Mg, Y and Sr.
Further preferably, Zr is added in the form of Mg — Zr alloy.
Preferably, in the step (1), the Mg, Y, Sr mixture is mixed in a high-frequency resistance melting furnace.
Preferably, in the step (1), the temperature for heating and melting is 700-.
Preferably, in the step (1), the temperature rise is 760-800 ℃; further preferably, in the step (1), the temperature for raising the temperature is 760-780 ℃.
Preferably, in the step (1), the standing time is 30-60 min.
Preferably, in the step (2), the stirring is performed by vacuum electromagnetic stirring. Compared with the stirring in other general modes, the stirring in the vacuum electromagnetic mode is to stir the magnesium alloy melt by an external electromagnetic field in a vacuum environment, so that the secondary pollution problem caused by an external stirring tool and the macro segregation and micro segregation phenomena of metal in the smelting process are avoided, the components of the magnesium alloy melt can be uniformly adjusted under the action of the external electromagnetic field, the temperature of the magnesium alloy melt is uniform, the burning loss of alloy components caused by local high temperature is avoided, and meanwhile, the stirring in the vacuum electromagnetic mode is efficient, energy-saving and pollution-free.
Preferably, in the step (2), the dross on the surface of the magnesium alloy melt is removed, then the magnesium alloy melt is kept stand and then cooled.
Preferably, in the step (2), the temperature for reducing the temperature is 700-.
Preferably, in the step (2), the mold is a metal mold.
Preferably, in the step (2), the cooling is performed by air cooling to room temperature (the room temperature is 10 to 35 ℃).
Preferably, the magnesium alloy produced in step (2) is a magnesium alloy ingot.
The third aspect of the invention provides application of degradable and tough magnesium alloy in manufacturing various devices, in particular medical devices.
Specifically, the equipment contains the magnesium alloy.
Preferably, the device is a medical device; further preferably, the apparatus is an instrument; more preferably, the device is a medical device.
Further preferably, the device is selected from any one of a vascular stent, a nerve conduit, an intraosseous screw, a cranial prosthesis, a vascular staple, and a tissue closure clip.
The invention also provides a magnesium alloy bar prepared from the magnesium alloy, in particular to a preparation method of the magnesium alloy bar, which comprises the following steps:
(1) carrying out solution treatment on the magnesium alloy to obtain a magnesium alloy blank, then carrying out first heat preservation, and carrying out first extrusion to obtain a magnesium alloy round bar;
(2) processing the magnesium alloy round bar prepared in the step (1) into a magnesium alloy round ingot (the conventional process in the field is to process the magnesium alloy round bar into the magnesium alloy round ingot), and coating a lubricant on the surface of the magnesium alloy round ingot;
(3) and (3) performing secondary heat preservation on the magnesium alloy round ingot treated in the step (2), and performing secondary extrusion and annealing treatment to obtain the magnesium alloy rod.
Preferably, in the step (1), the temperature of the solution treatment is 450-560 ℃, and the time of the solution treatment is 8-20 h.
Preferably, in the step (1), the solution treatment is carried out by taking out and air-cooling to room temperature (the room temperature is 10 to 35 ℃).
Preferably, in the step (1), before the solution treatment, the magnesium alloy is cut by the water saw, and after the solution treatment, the magnesium alloy is peeled by the machine (the peeling by the machine means that the surface of the magnesium alloy is removed by adopting a mechanical processing method).
Preferably, in the step (1), the temperature for the first heat preservation is 350-.
Preferably, in the step (1), the temperature of the first extrusion is 250-450 ℃.
Preferably, in the step (1), the speed of the first extrusion is 2-10 mm/s.
Preferably, in the step (1), the extrusion ratio of the first extrusion is 10 to 40.
Further preferably, in the step (1), the first extrusion is to place the magnesium alloy blank after the first heat preservation into an extrusion cylinder which is preheated (the temperature range of preheating is 250-. Wherein the temperature of the extrusion cylinder and the extrusion die is 250-450 ℃, the extrusion speed is 2-10mm/s, and the extrusion ratio is 10-40.
Preferably, in the step (1), the diameter of the magnesium alloy round rod is 20-60mm, and the length is 1000-3000 mm.
Preferably, in the step (2), the diameter of the magnesium alloy round ingot is 18-54mm, and the height is 20-60 mm.
Preferably, in the step (2), the lubricant (which is a high-temperature lubricant) is a mixture prepared by graphite mineral oil and molybdenum disulfide according to the mass ratio of (2-4) to 1; further preferably, in the step (2), the lubricant is a mixture prepared by graphite mineral oil and molybdenum disulfide according to the mass ratio of 3: 1.
Preferably, in the step (3), the temperature of the second heat preservation is 250-.
Preferably, in the step (3), the temperature of the second extrusion is 300-450 ℃.
Preferably, in the step (3), the speed of the second extrusion is 10-30 mm/s.
Preferably, in the step (3), the extrusion ratio of the second extrusion is 40 to 80.
Further preferably, in the step (3), the second extrusion is to place the magnesium alloy round ingot subjected to the second heat preservation into an extrusion cylinder preheated (the preheated temperature range is 300-. Wherein the temperature of the extrusion cylinder and the extrusion die is 300-450 ℃, the extrusion speed is 10-30mm/s, and the extrusion ratio is 40-80.
Compared with the prior art, the extrusion temperature during the second extrusion is reduced by 100-150 ℃, and the extrusion ratio is reduced by 20-50; the temperature of the extrusion cylinder and the extrusion die is reduced by 100-150 ℃ during extrusion; the extrusion force of the extruder is reduced by 20-40 tons during extrusion, and the extrusion speed is increased by 5-10 mm/s.
Preferably, in the step (3), in the annealing treatment, the annealing temperature is 200-400 ℃, the annealing time is 20-100min, and the cooling mode is to take out and cool the annealing material to room temperature (the room temperature is 10-35 ℃).
Preferably, the annealing treatment in step (3) is performed in an inert gas (e.g., argon) atmosphere.
Preferably, in the step (3), the magnesium alloy rod has a diameter of 4-12mm and a length of 1000-5000 mm.
The magnesium alloy rod has good application value in the field of medical instruments.
Compared with the prior art, the invention has the following beneficial effects:
(1) the magnesium alloy contains Y and Sr, which is beneficial to reducing the process conditions (temperature, pressure and the like) of the magnesium alloy in the plastic processing process, not only can the plastic processing of the magnesium alloy become easy to operate, but also the mechanical properties of instruments with various shapes obtained after the plastic processing are obviously improved, and the application of the magnesium alloy in the medical field is facilitated.
(2) The magnesium alloy has uniform components, compact structure and less internal defects such as air hole inclusion, and the like, so that a magnesium alloy rod with high quality can be obtained in the subsequent processing process.
(3) The tensile strength of the magnesium alloy bar prepared by the invention can reach 356MPa, the yield strength can reach 243MPa, and the requirements of orthopedic implantation instruments on mechanical properties are met.
(4) The magnesium alloy bar prepared by the invention has no obvious cytotoxicity and good blood compatibility through the result of biological tests, and meets the requirement of an orthopedic implant instrument on biocompatibility.
(5) The magnesium alloy bar prepared by the method has no welding area after shunting, and has good service performances such as mechanical property, degradation property and the like.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1: preparation of magnesium alloy
A degradable, tough magnesium alloy comprises the following components in percentage by mass:
a preparation method of degradable and tough magnesium alloy comprises the following steps:
(1) mixing Mg, Y, Sr, Zn and Zr in a tetrafluoroethane gas atmosphere, heating to 700 ℃ for melting, then heating to 760 ℃, and standing for 40min to obtain a magnesium alloy melt;
(2) and (2) stirring the magnesium alloy melt prepared in the step (1) in a vacuum electromagnetic mode, removing scum on the surface of the magnesium alloy melt, standing for 30min in a tetrafluoroethane gas atmosphere, then cooling to 700 ℃, pouring into a metal mold, and air-cooling to room temperature (the room temperature is 20 ℃) to prepare the magnesium alloy.
Example 2: preparation of magnesium alloy
A degradable, tough magnesium alloy comprises the following components in percentage by mass:
a preparation method of degradable and tough magnesium alloy comprises the following steps:
(1) mixing Mg, Y, Sr, Zn and Zr in a tetrafluoroethane gas atmosphere, heating to 720 ℃ for melting, then heating to 780 ℃, and standing for 30min to obtain a magnesium alloy melt;
(2) and (2) stirring the magnesium alloy melt prepared in the step (1) in a vacuum electromagnetic mode, removing scum on the surface of the magnesium alloy melt, standing for 40min in a tetrafluoroethane gas atmosphere, then cooling to 710 ℃, pouring into a metal mold, and air-cooling to room temperature (the room temperature is 25 ℃) to prepare the magnesium alloy.
Example 3: preparation of magnesium alloy
A degradable, tough magnesium alloy comprises the following components in percentage by mass:
Y 2％
Sr 2％
and the balance of Mg.
A preparation method of degradable and tough magnesium alloy comprises the following steps:
(1) mixing Mg, Y and Sr in a tetrafluoroethane gas atmosphere, heating to 710 ℃ for melting, then heating to 770 ℃, and standing for 40min to obtain a magnesium alloy melt;
(2) and (2) stirring the magnesium alloy melt prepared in the step (1) in a vacuum electromagnetic mode, removing scum on the surface of the magnesium alloy melt, standing for 60min in a tetrafluoroethane gas atmosphere, then cooling to 705 ℃, pouring into a metal mold, and air cooling to room temperature (the room temperature is 15 ℃) to prepare the magnesium alloy.
Example 4: preparation of magnesium alloy bar
A preparation method of a magnesium alloy bar comprises the following steps:
(1) performing water saw cutting and solution treatment on the magnesium alloy prepared in the embodiment 1, wherein the temperature of the solution treatment is 450 ℃, the time of the solution treatment is 10 hours, the cooling mode in the solution treatment is to take out the magnesium alloy to be air-cooled to room temperature of 20 ℃, then peeling the magnesium alloy by a machine to obtain a magnesium alloy blank, then performing primary heat preservation, the temperature of the primary heat preservation is 400 ℃, the time of the primary heat preservation is 1 hour, and then performing primary extrusion, wherein the primary extrusion is to place the magnesium alloy blank subjected to the primary heat preservation into a preheated extrusion cylinder, then extruding the magnesium alloy blank by using a horizontal hydraulic press, the magnesium alloy blank does not generate shunting and welding phenomena in the extrusion process, the temperature of the extrusion cylinder and the extrusion die is 300 ℃, the extrusion speed is 5mm/s, and the extrusion ratio is 10, so as to prepare a magnesium alloy round rod;
(2) processing the magnesium alloy round bar prepared in the step (1) into a magnesium alloy round ingot (the processing of the magnesium alloy round bar into the magnesium alloy round ingot is a conventional process in the field), and coating a lubricant on the surface of the magnesium alloy round ingot, wherein the lubricant is a mixture prepared from graphite mineral oil and molybdenum disulfide according to a mass ratio of 3: 1;
(3) and (3) performing secondary heat preservation on the magnesium alloy round ingot treated in the step (2), wherein the temperature of the secondary heat preservation is 250 ℃, the heat preservation time is 2 hours, performing secondary extrusion, wherein the secondary extrusion is to place the magnesium alloy round ingot subjected to the secondary heat preservation into a pre-heated extrusion cylinder, then extruding the magnesium alloy round ingot by using a horizontal hydraulic press, and the magnesium alloy round ingot is not subjected to shunting and welding phenomena in the extrusion process, wherein the temperature of the extrusion cylinder and an extrusion die is 350 ℃, the extrusion speed is 20mm/s, the extrusion ratio is 40, annealing treatment is performed in an argon atmosphere, the annealing temperature is 300 ℃, the annealing time is 50min, the cooling mode is to take out and cool the magnesium alloy round ingot to the room temperature of 20 ℃, and the magnesium alloy rod is prepared, and has the diameter of 6mm and the length of 1000 mm.
Example 5: preparation of magnesium alloy bar
A preparation method of a magnesium alloy bar comprises the following steps:
(1) performing water saw cutting and solution treatment on the magnesium alloy prepared in the embodiment 2, wherein the temperature of the solution treatment is 500 ℃, the time of the solution treatment is 15 hours, the cooling mode in the solution treatment is to take out the magnesium alloy and cool the magnesium alloy to room temperature of 20 ℃, then peeling the magnesium alloy by a machine to obtain a magnesium alloy blank, performing primary heat preservation, the temperature of the primary heat preservation is 380 ℃, the time of the primary heat preservation is 1.5 hours, and performing primary extrusion, wherein the primary extrusion is to place the magnesium alloy blank subjected to the primary heat preservation into a preheated extrusion cylinder and then extrude the magnesium alloy blank by using a horizontal hydraulic press, the magnesium alloy blank does not generate shunting and welding phenomena in the extrusion process, the temperature of the extrusion cylinder and the extrusion die is 320 ℃, the extrusion speed is 6mm/s, and the extrusion ratio is 12, so as to prepare a magnesium alloy round rod;
(2) processing the magnesium alloy round bar prepared in the step (1) into a magnesium alloy round ingot (the processing of the magnesium alloy round bar into the magnesium alloy round ingot is a conventional process in the field), and coating a lubricant on the surface of the magnesium alloy round ingot, wherein the lubricant is a mixture prepared from graphite mineral oil and molybdenum disulfide according to a mass ratio of 3: 1;
(3) and (3) performing secondary heat preservation on the magnesium alloy round ingot treated in the step (2), wherein the temperature of the secondary heat preservation is 300 ℃, the heat preservation time is 2 hours, performing secondary extrusion, wherein the secondary extrusion is to place the magnesium alloy round ingot subjected to the secondary heat preservation into a pre-heated extrusion cylinder, then extruding the magnesium alloy round ingot by using a horizontal hydraulic press, and the magnesium alloy round ingot is not subjected to shunting and welding phenomena in the extrusion process, wherein the temperature of the extrusion cylinder and an extrusion die is 360 ℃, the extrusion speed is 22mm/s, the extrusion ratio is 50, annealing treatment is performed in an argon atmosphere, the annealing temperature is 350 ℃, the annealing time is 60min, the cooling mode is to take out and cool the magnesium alloy round ingot to the room temperature of 20 ℃, and the magnesium alloy rod is prepared, and has the diameter of 6mm and the length of 1000 mm.
Example 6: preparation of magnesium alloy bar
A preparation method of a magnesium alloy bar comprises the following steps:
(1) performing water saw cutting and solution treatment on the magnesium alloy prepared in the embodiment 3, wherein the temperature of the solution treatment is 480 ℃, the time of the solution treatment is 13 hours, the cooling mode in the solution treatment is to take out the magnesium alloy to be air-cooled to room temperature of 20 ℃, then peeling the magnesium alloy by a machine to obtain a magnesium alloy blank, then performing primary heat preservation, the temperature of the primary heat preservation is 410 ℃, the time of the primary heat preservation is 1.5 hours, and then performing primary extrusion, wherein the primary extrusion is to place the magnesium alloy blank subjected to the primary heat preservation into a preheated extrusion cylinder, then extruding the magnesium alloy blank by using a horizontal hydraulic press, and the magnesium alloy blank does not generate shunting and welding phenomena in the extrusion process, wherein the temperature of the extrusion cylinder and the extrusion die is 350 ℃, the extrusion speed is 7mm/s, and the extrusion ratio is 18, so as to prepare a magnesium alloy round rod;
(2) processing the magnesium alloy round bar prepared in the step (1) into a magnesium alloy round ingot (the processing of the magnesium alloy round bar into the magnesium alloy round ingot is a conventional process in the field), and coating a lubricant on the surface of the magnesium alloy round ingot, wherein the lubricant is a mixture prepared from graphite mineral oil and molybdenum disulfide according to a mass ratio of 3: 1;
(3) and (3) performing secondary heat preservation on the magnesium alloy round ingot treated in the step (2), wherein the temperature of the secondary heat preservation is 310 ℃, the heat preservation time is 2 hours, performing secondary extrusion, wherein the secondary extrusion is to place the magnesium alloy round ingot subjected to the secondary heat preservation into a pre-heated extrusion cylinder, then extruding the magnesium alloy round ingot by using a horizontal hydraulic press, and the magnesium alloy round ingot is not subjected to shunting and welding phenomena in the extrusion process, wherein the temperature of the extrusion cylinder and an extrusion die is 380 ℃, the extrusion speed is 25mm/s, the extrusion ratio is 55, annealing treatment is performed in an argon atmosphere, the annealing temperature is 350 ℃, the annealing time is 60min, the cooling mode is to take out and cool the magnesium alloy round ingot to the room temperature of 20 ℃, and the magnesium alloy rod is prepared, and has the diameter of 6mm and the length of 1000 mm.
Comparative example 1
In comparison with example 1, the magnesium alloy in comparative example 1 does not contain Y and Sr, and the remaining components and the manufacturing method are the same as those of example 1, and the magnesium alloy obtained is a magnesium alloy rod according to the method of example 4.
Comparative example 2
In comparison with example 2, the magnesium alloy in comparative example 2 does not contain Y, and the remaining components and the production method are the same as those of example 2, and the magnesium alloy obtained is a magnesium alloy rod according to the method of example 5.
Comparative example 3
In comparison with example 3, the magnesium alloy in comparative example 3 does not contain Sr, and the remaining components and the manufacturing method are the same as those of example 3, and the magnesium alloy obtained is a magnesium alloy rod according to the method of example 6.
Product effectiveness testing
The magnesium alloy rods prepared in examples 4 to 6 and comparative examples 1 to 3 were tested for tensile strength, yield strength, elongation and degradation in simulated body fluid, and the results are shown in table 1.
Table 1: results of Performance testing
As can be seen from Table 1, the tensile strength, yield strength and elongation of the magnesium alloy rods prepared in examples 4 to 6 of the present invention are significantly superior to those of the magnesium alloy rods prepared in comparative examples 1 to 3. The selection of the element types in the magnesium alloy has obvious influence on the mechanical property of the magnesium alloy bar. The degradation modes of the magnesium alloy rods prepared in the embodiments 4 to 6 of the invention are all uniform degradation, which is obviously superior to the degradation modes of the magnesium alloy rods prepared in the comparative examples 1 to 3, i.e. the magnesium alloy rods prepared in the embodiments 4 to 6 of the invention have good degradation performance.
Claims (15)
1. A magnesium alloy comprising Mg, characterized by further comprising the following components in mass fraction:
Y 0.4-8.0％
Sr 0.1-6.0％。
2. the magnesium alloy according to claim 1, further comprising Zn and/or Zr.
3. The magnesium alloy according to claim 2, wherein Zn is 0.1 to 6.0% by mass; zr is 0.1 to 5.0 percent.
4. The magnesium alloy according to claim 1, comprising the following components in mass fraction:
5. magnesium alloy according to claim 1, characterized in that the magnesium alloy, in addition to containing Mg, Y, Sr, Zn, Zr, comprises in total < 0.05% of other elements in mass fraction.
6. The magnesium alloy of claim 5, wherein the other element comprises at least one of Fe, Cu, or Ni.
7. The method for producing a magnesium alloy according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) mixing Mg, Y and Sr in a protective gas atmosphere, heating to melt, then heating, and standing to obtain a magnesium alloy melt;
(2) and (2) stirring the magnesium alloy melt prepared in the step (1), removing scum on the surface of the magnesium alloy melt, cooling, pouring into a mold, and cooling to prepare the magnesium alloy.
8. The production method according to claim 7, wherein in the step (1), the protective gas is tetrafluoroethane.
9. The method according to claim 7, wherein Zn and/or Zr is further added during the mixing of Mg, Y and Sr in the step (1).
10. The production method according to claim 7, wherein in the step (1), Y is added in the form of an Mg-Y alloy; sr is added in the form of Mg-Sr alloy.
11. The method as claimed in claim 7, wherein the temperature of the step (1) is raised to 760-800 ℃.
12. An apparatus comprising the magnesium alloy according to any one of claims 1 to 6.
13. The apparatus according to claim 12, wherein the apparatus is selected from any one of a vascular stent, a nerve conduit, an endosseous screw, a cranial prosthesis, a vascular staple, a tissue closure clip.
14. The preparation method of the magnesium alloy bar is characterized by comprising the following steps:
(1) carrying out solution treatment on the magnesium alloy as defined in any one of claims 1 to 6 to obtain a magnesium alloy blank, then carrying out first heat preservation, and carrying out first extrusion to obtain a magnesium alloy round rod;
(2) processing the magnesium alloy round bar prepared in the step (1) into a magnesium alloy round ingot, and coating a lubricant on the surface of the magnesium alloy round ingot;
(3) and (3) performing secondary heat preservation on the magnesium alloy round ingot treated in the step (2), and performing secondary extrusion and annealing treatment to obtain the magnesium alloy rod.
15. The method as claimed in claim 14, wherein the temperature of the second extrusion in step (3) is 300-450 ℃; the extrusion ratio of the second extrusion is 40-80.
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