CN114107712A - Medical magnesium-based composite material bar and preparation method thereof - Google Patents
Medical magnesium-based composite material bar and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a medical magnesium-based composite material bar and a preparation method thereof, and Mg is prepared by an in-situ liquid phase metallurgy method2Heating the composite material to a semi-solid state region, keeping the temperature, quenching to obtain a semi-solid state tissue blank, and refining primary or eutectic Mg2Si particles spheroidized and a second phase is solid-dissolved into the matrix; and then heating the blank, and carrying out hot extrusion to obtain the magnesium-based composite material bar with excellent mechanical property and controllable degradation rate. The invention improves the plastic deformation capacity of the composite material through semi-solid treatment and greatly improves the subsequent processThe yield and the production process stability of the product are improved; the mechanical property and the biodegradation rate of the medical magnesium-based composite material bar can be flexibly and accurately regulated and controlled by regulating and controlling the semi-solid parameters and the hot extrusion deformation conditions, and the degradation of the material in body fluid can be controlled more safely, reliably and efficiently.
Description
Technical Field
The invention belongs to the technical field of preparation of medical magnesium-based materials, and particularly relates to a medical magnesium-based composite material bar and a preparation method thereof.
Background
At present, the clinical medical metal materials mainly comprise stainless steel, titanium alloy, zinc alloy and the like. However, these materials have the problems of high density, difficult degradation and the like, the medical implant device needs to be taken out by a secondary operation, the pain and the economic burden of a patient are increased, and the mechanical property of the metal materials is higher than that of bone tissues, so that the stress shielding effect is easily generated, and the peripheral bone tissues are stimulated by stress and are incompletely healed. Magnesium is an indispensable nutrient element for human body, and has a density of about 1.74g/cm3And the density of human bone is 1.75g/cm3Are very close; in addition, the elastic modulus of the magnesium alloy is about 45GPa, the magnesium alloy is similar to human bone tissues, the magnesium alloy can effectively reduce stress when used as an implant material, and can be gradually degraded in body fluid in the healing process of the human tissues, and Mg ions generated by degradation can participate in metabolism and be discharged out of the body or directly absorbed by surrounding tissues. Therefore, the magnesium alloy has the advantages of degradability, mechanical property matching, good biological safety and the like as medical implantation instruments such as bone nails, intravascular stents and the like, and has wide application prospect in the medical field.
However, the medical magnesium alloy has the problems of too fast degradation rate and poor lasting mechanical property in the application process. At present, the better method for improving the mechanical property of the magnesium alloy is to add hard phase particles with high hardness and high modulus into the magnesium alloy to obtain the particle reinforced magnesium matrix composite. Mg (magnesium)2The Si intermetallic compound particles have high modulus (120GPa), high melting point (1085 ℃), low coefficient of thermal expansion and density close to that of magnesium alloy (1.99 g/cm)3) And become reinforcing particles commonly used in magnesium alloys. Mg (magnesium)2The Si particles can be formed in situ in the magnesium alloy melt by a liquid phase metallurgical method, i.e. a certain amount of Si source is added into the magnesium alloy melt and reacts with Mg to form Mg in the solidification process2A Si hard phase; utensil for cleaning buttockHas the advantages of good particle dispersibility, high chemical stability, good combination of hard phase and matrix, simple preparation process, and the like. However, nascent Mg formed2The Si has larger particle size and is dendritic and eutectic Mg2Si is in a Chinese character shape, and although the strength of the composite material is improved, the plasticity is reduced, the subsequent plastic forming is difficult, and the yield is low.
In addition, the medical magnesium alloy has a degradation rate which is too high after being implanted, so that the integrity of the device is damaged during service, and a large amount of bubbles are generated in a short time to cause the swelling and necrosis of surrounding tissues. The research on the published documents shows that the corrosion resistance of the magnesium alloy material can be improved by refining the crystal grains, and the degradation rate of the implanted magnesium alloy is further regulated and controlled. The plastic processing can obviously refine grains, greatly improve the mechanical property and reduce the degradation rate of the material. Due to Mg2The problem of coarse Si particle size leads to difficulties in deformation during hot working (e.g. extrusion, rolling and forging), especially brittle Mg2Si dendrite fractures to form a large number of cracks, so that the yield of products is low, and the service mechanical property and the corrosion resistance are reduced due to the residual cracks. By refining Mg2The Si particle size can improve medical Mg2The formability and degradation rate of the Si/Mg composite material. At present, there is a great deal of improvement in Mg2The method for enhancing the shape and size of the particles by Si, such as high-energy ultrasonic treatment, addition of trace alloy elements and the like, has complex process and needs equipment with high added value, and particularly, the added alloy elements are harmful to human bodies.
The problems of how to improve the mechanical property, corrosion resistance, degradation rate and the like of the medical magnesium-based implant material become a research hotspot for the wide use of magnesium alloy materials as biomedical materials at the present stage.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a medical magnesium-based composite bar and a preparation method thereof aiming at the defects in the prior art, so that the size and the shape of a reinforcing phase of a medical particle reinforced magnesium-based composite are improved, the plastic deformation capacity is improved, the magnesium-based composite with excellent mechanical property and controllable degradation rate is obtained through hot processing, and the medical magnesium-based composite bar can be used for medical implantation instruments such as bone nails, intravascular stents and the like.
The invention adopts the following technical scheme:
a preparation method of a medical magnesium-based composite bar comprises the following steps:
s1, heating and melting Mg, Mg-Si intermediate alloy, Al and Zn ingots and electrolytic Mn sheets, and carrying out heat preservation treatment to obtain a melt A;
s2, adding a refining agent into the melt A prepared in the step S1, stirring, standing, and casting to obtain a cast ingot;
s3, heating the ingot prepared in the step S2 to a semi-solid temperature range in a vacuum environment, preserving heat, and then putting the ingot into a cooling medium for cooling to obtain a semi-solid blank;
s4, hot extruding the semi-solid blank prepared in the step S3 to obtain the medical magnesium-based composite material bar.
Specifically, in step S1, the temperature rise is 700 to 750 ℃, the temperature rise environment is under the protection of argon, and the heat preservation time is 10 to 30 min.
Specifically, in step S2, the refining agent contains 30 to 36 wt.% NaCl and 20 to 28 wt.% CaF236 to 44 wt.% MgCl2The components of the ingot comprise, by mass, 4.2-8.9% of Al, 0.8-3.8% of Zn, 0.2-0.5% of Mn and 1-6.5% of Mg2Si and the balance of Mg.
Specifically, in step S2, the standing time is 20-40 min, the casting temperature is 700-720 ℃, and the preheating temperature of the mold before casting is 200-350 ℃.
Specifically, in step S3, the semi-solid temperature range is 550-600 ℃, and the heat preservation time is 10-60 min.
Specifically, in step S3, the cooling medium is water with a temperature of 60 to 100 ℃.
Specifically, in step S4, the semi-solid blank has a diameter of 20 to 80mm and a thickness of 50 to 100 mm.
Specifically, in step S4, the heating temperature of the hot extrusion is 250 to 420 ℃, and the preheating temperature of the semi-solid blank before heating is 250 to 420 ℃.
Specifically, the weight percentage of the composition comprises 3.1 to 8.9 percent of Al, 0.8-5.9% of Zn, 0.2-0.5% of Mn and 1-6.5% of Mg2Si and the balance of Mg.
Furthermore, the diameter of the medical magnesium-based composite material bar is 5-30 mm.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention relates to a preparation method of a medical magnesium-based composite bar, which prepares Mg by an in-situ liquid phase metallurgy method2Heating the composite material to a semi-solid state region, keeping the temperature, quenching to obtain a semi-solid state tissue blank, performing hot extrusion on the blank to obtain a magnesium-based composite material bar with excellent mechanical property and controllable degradation rate, and adding Mg to the bar2The Si reinforced magnesium-based composite material is heated to a semi-solid region for heat preservation and quenching to obtain a semi-solid blank, and primary or eutectic Mg can be refined2Si particles are spheroidized, and a second phase can be dissolved into a matrix in a solid mode, so that the plastic deformation capacity of the composite material is remarkably improved, and the yield of the subsequent process and the process stability of production are greatly improved; according to specific use requirements, the mechanical property and the biodegradation rate of the medical magnesium-based composite material bar can be flexibly and accurately regulated and controlled by regulating and controlling semi-solid parameters and hot extrusion deformation conditions, and the degradation of the material in body fluid can be controlled more safely, reliably and efficiently.
Furthermore, the temperature rise is 700-750 ℃ and higher than the melting point of pure magnesium, so that the cast ingot is melted, and the burning loss and oxidation in the melt higher than 750 ℃ are aggravated, so that the component design is inaccurate and impurities are increased; the heat preservation time is 10-30 min, so that the added alloy elements are fully dissolved and uniformly distributed in the melt, and the time is not too long, which can cause the increase of burning loss.
Furthermore, the refining agent in the corresponding component range is used, so that the oxide inclusions in the melt can float up or sink, the gas in the melt can be removed, the melt is refined, and the purity and the performance of the material are improved.
Further, standing ensures that the refined oxide inclusions float up to the surface of the melt or sink to the bottom of the crucible, the casting temperature is 700-720 ℃, is higher than the melting point, but is lower than the melting temperature, ensures that the melt has better fluidity and avoids oxidation caused by overhigh temperature during casting. The metal liquid is cooled too fast when the mould is not preheated, the fluidity is reduced violently, and the defects of cold shut, unsatisfied pouring, inclusion, air holes and the like of a casting are easy to occur, so that the mould is preheated, but the temperature is not too high, the solidification speed is reduced due to too high temperature, crystal grains are large, and the performance is not good.
Furthermore, liquid phase appears in the Mg-Al alloy at 550-600 ℃, the quantity of the liquid phase is increased when the temperature is higher than the interval, the material is melted, and if the temperature is too low, the slow dendritic Mg is diffused too much2Si cannot be spheroidized; the heat preservation time is 10-60min, the element diffusion and Mg are ensured2Si is fully spheroidized, and excessively long matrix grains grow seriously, so that the performance is poor.
Furthermore, warm water cooling can reduce the temperature of the sample, keep semi-solid tissues, and simultaneously, the cooling speed is lower than that of cold water, so that the sample is prevented from being hot cracked in the cooling process.
Furthermore, the extrusion die and the semi-solid blank are heated to improve the plastic deformation capacity of the material, and dynamic recrystallization occurs at the temperature to refine the grains. The material is softened seriously at the over-high temperature and is easy to crack, and the over-low temperature is lower than the dynamic recrystallization temperature, so that the obvious grain refinement effect cannot be generated.
A medical magnesium-based composite material bar comprises, by mass, 3.1% -8.9% of Al, 0.8% -5.9% of Zn, 0.2% -0.5% of Mn and 1-6.5% of Mg2Si and the balance of Mg. The components ensure that the composite material has better strength, the price of various elements is low, the biocompatibility of the medical magnesium-based composite material bar material is high, and the composite material bar material is particularly suitable for medical implantation instruments such as medical materials of bone nails, intravascular stents, human skeleton implants and the like.
Furthermore, the size of the semi-solid blank and the design of the extrusion bar are designed according to the parameters of an experimental die, so that the deformation is provided, and the crystal grains are refined.
In summary, Mg is added2The Si reinforced magnesium-based composite material is heated to a semi-solid region for heat preservation and quenching to obtain a semi-solid blank, and primary or eutectic Mg can be refined2The particles of Si are formed by the sintering of the silicon,spheroidizing the composite material, and dissolving a second phase into a matrix in a solid manner, so that the plastic deformation capacity of the composite material is remarkably improved, and the yield of the subsequent process and the process stability of production are greatly improved; according to specific use requirements, the mechanical property and the biodegradation rate of the medical magnesium-based composite material bar can be flexibly and accurately regulated and controlled by regulating and controlling semi-solid parameters and hot extrusion deformation conditions, and the degradation of the material in body fluid can be controlled more safely, reliably and efficiently.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
Fig. 1 is an optical microscopic structure view of a semi-solid billet in example 2;
fig. 2 is a macroscopic photograph of the magnesium-based composite material bar for chinese medicine of example 2.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
As used herein, the term "and/or" refers to any and all possible combinations of one or more of the associated listed items and includes such combinations.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
The invention provides a medical magnesium-based composite material bar and a preparation method thereof, and Mg is prepared by an in-situ liquid phase metallurgy method2Heating the composite material to a semi-solid state region, keeping the temperature, quenching to obtain a semi-solid state tissue blank, and refining primary or eutectic Mg2Si particles spheroidized and a second phase is solid-dissolved into the matrix; then heating the blank, carrying out hot extrusion to obtain the magnesium-based composite material bar with excellent mechanical property and controllable degradation rate, improving the plastic deformation capacity of the composite material through semi-solid treatment, and greatly improving the yield of the subsequent process and the process stability of production; the mechanical property and the biodegradation rate of the medical magnesium-based composite material bar can be flexibly and accurately regulated and controlled by regulating and controlling the semi-solid parameters and the hot extrusion deformation conditions, and the degradation of the material in body fluid can be controlled more safely, reliably and efficiently. The prepared medical magnesium-based composite bar has high biocompatibility, and is particularly suitable for medical implantation instruments such as medical materials of bone nails, intravascular stents, human skeleton implants and the like.
The invention relates to a preparation method of a medical magnesium-based composite bar, which comprises the following steps:
s1, adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating and melting under the protection of argon, and preserving heat for 10-30 min;
the melting temperature of the magnesium alloy raw material is 700-750 ℃.
S2, adding a refining agent, stirring vigorously, standing, removing surface scum, and casting into a preheated low-carbon steel mold to obtain a cast ingot;
the refining agent comprises 30-36 wt.% of NaCl and 20-28 wt.% of CaF236 to 44 wt.% MgCl2Standing for 20-40 min, casting at 700-720 ℃, preheating at 200-350 ℃, and ingot casting comprising, by mass, 4.2-8.9% of Al, 0.8-3.8% of Zn, 0.2-0.5% of Mn, and 1-6.5% of Mg2Si and the balance of Mg.
S3, putting the cast ingot in the step S2 into a vacuum resistance furnace, heating to a semi-solid interval, keeping the temperature for a period of time, quickly taking out the cast ingot, putting the cast ingot into a cooling medium, and cooling to obtain a semi-solid blank;
the semi-solid temperature of the semi-solid blank is 550-600 ℃, the heat preservation time is 10-60min, and the cooling medium is water with the temperature of 60-100 ℃.
S4, processing the blank obtained in the step S3 into a cylinder, grinding and polishing the surface of the cylinder, and putting the cylinder into an extrusion cylinder for hot extrusion to obtain the medical magnesium-based composite material bar with fine and uniform tissue.
The processing size diameter of an original cylindrical blank is 20-80 mm, the thickness is 50-100 mm, the blank preheating temperature is 250-420 ℃, and the extrusion container heating temperature is 250-420 ℃; the diameter range of the extruded bar is 5-30 mm.
The medical magnesium-based composite material bar prepared by the invention comprises, by mass, 3.1% -8.9% of Al, 0.8% -5.9% of Zn, 0.2% -0.5% of Mn and 1-6.5% of Mg2Si, and the balance being Mg; can be used for implanting instruments such as bone nails and intravascular stents, and has excellent mechanical property and controllable degradation rate; and, by adjusting Mg2The magnesium-based material with different mechanical properties and degradation rates is obtained by the Si strengthening phase content, the semi-solid state process and the hot extrusion parameters, and can be flexibly applied to medical implant materials under various use conditions.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating to 700 ℃ under the protection of argon gas for melting, and preserving heat for 30 min; adding refining agent (30 wt.% NaCl, 28 wt.% CaF)242 wt.% MgCl2) Stirring vigorously, standing for 20min, removing surface scum, and casting into low carbon steel mold preheated to 200 deg.C at 700 deg.C to obtain ingot;
the chemical components of the cast ingot comprise, by mass, 8.9% of Al, 0.8% of Zn, 0.2% of Mn and 1% of Mg2Si and the balance of Mg.
Putting the cast ingot into a vacuum resistance furnace, heating to 550 ℃ to enable part of liquid phase to appear in the tissue, keeping the temperature for 60min, quickly taking out the cast ingot, putting the cast ingot into water at 60 ℃ and cooling to obtain semi-solid blank; processing the obtained blank into a cylinder with the diameter of 20mm, grinding and polishing the surface of the blank, and preheating the blank at 250 ℃; putting the medical magnesium-based composite material into an extrusion cylinder for hot extrusion, wherein the heating temperature of the extrusion cylinder is 250 ℃, and obtaining a medical magnesium-based composite material bar with fine and uniform tissue, and the diameter of the extruded bar is 5 mm; the bar is further processed to be used as a medical implant material.
In this example, a small amount of Mg2The Si phase is completely spheroidized under the semi-solid condition and extruded under the low-temperature medium deformation condition, and the grain size of the material is extremely small, so that the material has medium strength and excellent plasticity. The extruded composite material has excellent corrosion resistance due to the small content of the strengthening phase. Simultaneously, completely spheroidized Mg2Si provides excellent plastic formability and extremely high material yield.
Example 2
Adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating to 720 ℃ under the protection of argon gas for melting, and preserving heat for 20 min; adding refining agent (containing NaCl 32 wt.% and CaF 24 wt.%)244 wt.% MgCl2) Violently stirring, standing for 30min, removing surface scum, and casting into a low-carbon steel mold preheated to 300 ℃ at 710 ℃ to obtain a cast ingot;
the chemical components of the cast ingot comprise 6.1 percent of Al, 1.8 percent of Zn, 0.3 percent of Mn and 3.5 percent of Mg by mass percentage2Si and the balance of Mg.
Putting the cast ingot into a vacuum resistance furnace, heating to 580 ℃ to enable part of liquid phase to appear in the tissue, keeping the temperature for 30min, quickly taking out the cast ingot, and putting the cast ingot into 70 ℃ water for cooling to obtain semi-solid blank; processing the obtained blank into a cylinder with the diameter of 50mm, grinding and polishing the surface of the blank, and preheating the blank to 380 ℃; putting the medical magnesium-based composite material into an extrusion cylinder for hot extrusion, wherein the heating temperature of the extrusion cylinder is 380 ℃, and obtaining a medical magnesium-based composite material bar with fine and uniform tissue, wherein the diameter of the extruded bar is 15 mm; the bar is further processed to be used as a medical implant material.
Referring to FIG. 1, the semi-solid structure of example 2 shows dendritic Mg2Most of the Si is spheroidized, and only a few of the Si is not spheroidized.
FIG. 2 is a photomicrograph of an extruded bar, with no surface cracks, illustrating Mg under this process2The Si appearance is obviously improved, so that the plastic forming performance of the composite material is excellent. Lower Mg2Si content and spheroidizing to make the composite material plasticAnd excellent corrosion resistance.
Example 3
Adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating to 750 ℃ under the protection of argon gas for melting, and preserving heat for 10 min; adding refining agent (containing 33 wt.% NaCl and 26 wt.% CaF)241 wt.% MgCl2) Stirring vigorously, standing for 40min, removing surface scum, and casting at 720 deg.C into low carbon steel mold preheated to 350 deg.C to obtain ingot;
the chemical components of the cast ingot comprise, by mass, 4.2% of Al, 3.8% of Zn, 0.5% of Mn and 6.5% of Mg2Si and the balance of Mg.
And (3) putting the cast ingot into a vacuum resistance furnace, heating to 600 ℃ to enable a part of liquid phase to appear in the tissue, keeping the temperature for 10min, quickly taking out the cast ingot, and putting the cast ingot into water at 80 ℃ for cooling to obtain a semi-solid blank. Processing the obtained blank into a cylinder with the diameter of 80mm, grinding and polishing the surface of the blank, and preheating the blank at 420 ℃; putting the medical magnesium-based composite material into an extrusion cylinder for hot extrusion, wherein the heating temperature of the extrusion cylinder is 420 ℃, and obtaining a medical magnesium-based composite material bar with fine and uniform tissue, and the diameter of the extruded bar is 30 mm; the bar material can be used as medical implant material after being processed by fine processing.
Under the condition of the embodiment, the semi-solid temperature is higher, a small amount of liquid phase appears, the diffusion of elements can be accelerated, and Mg2Si can be fully spheroidized, the content is higher, and the hardness and the strength of the composite material are higher; the subsequent hot extrusion deformation is small and the temperature is high, the material densification is realized, the grain size of the final composite material is in a medium level, the strength of the composite material is high, the plasticity is moderate, and the corrosion resistance is excellent. Although Mg2Mg having a high Si content but being sufficiently spheroidized2Si and high extrusion temperature, low extrusion ratio result in high material yield.
Example 4
Adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating to 725 ℃ under the protection of argon, melting, and keeping the temperature for 25 min; adding refining agent (with 34 wt.% NaCl and 28 wt.% CaF)238 wt.% MgCl2) Stirring vigorously, standing for 15min, and removing surface scumCasting the cast ingot into a low-carbon steel mold preheated to 330 ℃ at 715 ℃ to obtain a cast ingot;
the chemical components of the cast ingot comprise 5.2 percent of Al, 2.1 percent of Zn, 0.4 percent of Mn and 4.5 percent of Mg by mass percentage2Si and the balance of Mg.
And (3) putting the cast ingot into a vacuum resistance furnace, heating to 585 ℃, enabling part of liquid phase to appear in the tissue, keeping the temperature for 15min, quickly taking out the cast ingot, and putting the cast ingot into hot water at 75 ℃ for cooling to obtain a semi-solid blank. Processing the obtained blank into a cylinder with the diameter of 60mm, grinding and polishing the surface of the blank, and preheating the blank to 380 ℃; putting the medical magnesium-based composite material into an extrusion cylinder for hot extrusion, wherein the heating temperature of the extrusion cylinder is 380 ℃, and obtaining a medical magnesium-based composite material bar with fine and uniform tissue, wherein the diameter of the extruded bar is 15 mm; the bar material can be used as medical implant material after being processed by fine processing.
The semi-solid temperature is at a moderate level, Mg under the conditions of this example2Most of Si can be spheroidized; subsequent hot extrusion has large deformation and low temperature, and finally the composite material has refined crystal grains, moderate strength, moderate plasticity and excellent corrosion resistance.
Example 5
Adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating to 705 ℃ under the protection of argon gas for melting, and preserving heat for 30 min; adding refining agent (35 wt.% NaCl, 27 wt.% CaF)238 wt.% MgCl2) Violently stirring, standing for 25min, removing surface scum, and casting into a low-carbon steel mold preheated to 315 ℃ at 705 ℃ to obtain a cast ingot;
the chemical components of the cast ingot comprise, by mass, 4.8% of Al, 1.5% of Zn, 0.3% of Mn and 4.0% of Mg2Si and the balance of Mg.
And putting the cast ingot into a vacuum resistance furnace, heating to 575 ℃ to enable a part of liquid phase to appear in the tissue, keeping the temperature for 35min, quickly taking out the cast ingot, and putting the cast ingot into hot water at 90 ℃ for cooling to obtain a semi-solid blank. Processing the obtained blank into a cylinder with the diameter of 50mm, grinding and polishing the surface of the blank, and preheating the blank at 330 ℃; putting the medical magnesium-based composite material into an extrusion cylinder for hot extrusion, wherein the heating temperature of the extrusion cylinder is 330 ℃, and obtaining a medical magnesium-based composite material bar with fine and uniform tissue, and the diameter of the extruded bar is 12 mm; the bar material can be used as medical implant material after being processed by fine processing.
In this example, the semi-solid state temperature was low and the Mg was kept warm for a long time2Basically spheroidizing Si; the subsequent hot extrusion has large deformation and low temperature, a large amount of nano-phase is separated out in the deformation, the crystal grains are obviously refined, and the composite material has extremely high strength, medium plasticity and moderate corrosion resistance. The larger extrusion ratio greatly increases the efficiency of the medical material production process.
Example 6
Adding pure Mg, Mg-Si intermediate alloy, pure Al, Zn ingots and an electrolytic Mn sheet into a resistance furnace, heating to 715 ℃ under the protection of argon gas for melting, and preserving heat for 25 min; adding refining agent (containing 29 wt.% NaCl and 28 wt.% CaF)243 wt.% MgCl2) Violently stirring, standing for 35min, removing surface scum, and casting into a low-carbon steel mold preheated to 315 ℃ at 705 ℃ to obtain a cast ingot;
the chemical components of the cast ingot comprise, by mass, 4.5% of Al, 2.8% of Zn, 0.2% of Mn and 3.5% of Mg2Si and the balance of Mg.
And putting the cast ingot into a vacuum resistance furnace, heating to 565 ℃ to enable part of liquid phase to appear in the tissue, keeping the temperature for 50min, quickly taking out the cast ingot, and putting the cast ingot into hot water of 100 ℃ for cooling to obtain a semi-solid blank. Processing the obtained blank into a cylinder with the diameter of 70mm, grinding and polishing the surface of the blank, and preheating the blank at 280 ℃; putting the medical magnesium-based composite material into an extrusion cylinder for hot extrusion, wherein the heating temperature of the extrusion cylinder is 280 ℃, and obtaining a medical magnesium-based composite material bar with fine and uniform tissue, wherein the diameter of the extruded bar is 15 mm; the bar material can be used as medical implant material after being processed by fine processing.
In this example, the semi-solid state temperature was low and the Mg was kept warm for a long time2Basically spheroidizing Si; the subsequent hot extrusion has large deformation and low temperature, a large amount of nano-phase is separated out in the deformation, finally the crystal grains of the composite material are obviously refined, and the composite material has extremely high strength, moderate hardness and plasticity and slow degradation rate. Deformation at low temperature requires Mg2The Si content is lower and the spheroidization is thorough, so that the later spheroidization can be ensuredAnd (5) continuous plastic processing yield. Therefore, the mechanical property and degradation rate of the medical magnesium-based composite material can be effectively regulated and controlled by designing the content of the reinforcing phase, the semi-solid parameters and the hot extrusion parameters, and the method can be suitable for various products.
In summary, the medical magnesium-based composite material bar and the preparation method thereof are prepared by mixing Mg2The Si reinforced magnesium-based composite material is heated to a semi-solid region for heat preservation and quenching to obtain a semi-solid blank, and primary or eutectic Mg can be refined2Si particles are spheroidized, and a second phase can be dissolved into a matrix in a solid mode, so that the plastic deformation capacity of the composite material is remarkably improved, and the yield of the subsequent process and the process stability of production are greatly improved; according to specific use requirements, Mg is regulated and controlled2The content of the Si strengthening phase, the semi-solid parameters and the hot extrusion deformation conditions can flexibly and accurately regulate and control the mechanical property and the biodegradation rate of the medical magnesium-based composite material bar, more safely, reliably and efficiently control the degradation of the material in body fluid, and can be flexibly applied to medical implant materials under various use conditions.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the medical magnesium-based composite bar is characterized by comprising the following steps:
s1, heating and melting Mg, Mg-Si intermediate alloy, Al and Zn ingots and electrolytic Mn sheets, and carrying out heat preservation treatment to obtain a melt A;
s2, adding a refining agent into the melt A prepared in the step S1, stirring, standing, and casting to obtain a cast ingot;
s3, heating the ingot prepared in the step S2 to a semi-solid temperature range in a vacuum environment, preserving heat, and then putting the ingot into a cooling medium for cooling to obtain a semi-solid blank;
s4, hot extruding the semi-solid blank prepared in the step S3 to obtain the medical magnesium-based composite material bar.
2. The method for preparing the medical magnesium-based composite material bar according to claim 1, wherein in the step S1, the temperature is raised to 700-750 ℃, the temperature raising environment is under argon protection, and the temperature keeping time is 10-30 min.
3. The method for preparing a medical magnesium-based composite material bar according to claim 1, wherein in step S2, the refining agent comprises 30-36 wt.% NaCl and 20-28 wt.% CaF236 to 44 wt.% MgCl2The components of the ingot comprise, by mass, 4.2-8.9% of Al, 0.8-3.8% of Zn, 0.2-0.5% of Mn and 1-6.5% of Mg2Si and the balance of Mg.
4. The method for preparing the medical magnesium-based composite material bar according to claim 1, wherein in the step S2, the standing time is 20-40 min, the casting temperature is 700-720 ℃, and the preheating temperature of the mold before casting is 200-350 ℃.
5. The method for preparing the medical magnesium-based composite material bar according to claim 1, wherein in the step S3, the semi-solid temperature is 550-600 ℃, and the heat preservation time is 10-60 min.
6. The method for preparing a medical magnesium-based composite material bar according to claim 1, wherein in step S3, the cooling medium is water with a temperature of 60-100 ℃.
7. The method for preparing a medical magnesium-based composite material bar according to claim 1, wherein in step S4, the semi-solid billet has a diameter of 20 to 80mm and a thickness of 50 to 100 mm.
8. The method for preparing a medical magnesium-based composite material bar according to claim 1, wherein in step S4, the heating temperature of hot extrusion is 250-420 ℃, and the preheating temperature of the semi-solid billet before heating is 250-420 ℃.
9. The medical magnesium-based composite material bar prepared by the method of claim 1, which comprises, by mass, 3.1-8.9% of Al, 0.8-5.9% of Zn, 0.2-0.5% of Mn and 1-6.5% of Mg2Si and the balance of Mg.
10. The medical magnesium-based composite bar according to claim 9, wherein the medical magnesium-based composite bar has a diameter of 5 to 30 mm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433862A (en) * | 2022-08-05 | 2022-12-06 | 太原理工大学 | Preparation method of Ni-free degradable magnesium-based material |
| CN115852223A (en) * | 2022-11-30 | 2023-03-28 | 西北有色金属研究院 | Preparation method of low-cost large-size ultrafine-grained biomedical magnesium-based composite material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002027053A1 (en) * | 2000-09-26 | 2002-04-04 | Kwang Seon Shin | High strength magnesium alloy and its preparation method |
| CN101285144A (en) * | 2008-05-05 | 2008-10-15 | 哈尔滨工程大学 | Magnesium alloy for semi-solid forming and preparation method of semi- solid blank |
| CN101306464A (en) * | 2008-05-23 | 2008-11-19 | 北京科技大学 | Process for preparing high performance structural member with high SiC grain volume fraction |
| CN101403063A (en) * | 2008-11-26 | 2009-04-08 | 南昌大学 | Process for producing in situ AM60 magnesium-base composite material semi-solid state |
| CN101514409A (en) * | 2009-03-31 | 2009-08-26 | 南昌大学 | A method for preparing in situ MgSi particle reinforced metal matrix composite |
| CN101979697A (en) * | 2010-11-19 | 2011-02-23 | 江苏大学 | Method for preparing Mg2Si particle-reinforced bulk magnesium-based amorphous alloy composite material |
| CN111534731A (en) * | 2020-05-25 | 2020-08-14 | 珠海中科先进技术研究院有限公司 | Particle-reinforced medical magnesium-based composite material semi-solid billet and preparation method thereof |
| CN112746194A (en) * | 2020-10-29 | 2021-05-04 | 哈尔滨理工大学 | Al (aluminum)2O3Method for particle reinforced magnesium-based composite material and application thereof |
| CN113231791A (en) * | 2021-03-23 | 2021-08-10 | 北京交通大学 | Magnesium-based composite material cylinder sleeve for motorcycle engine and preparation method thereof |
-
2021
- 2021-11-26 CN CN202111424898.1A patent/CN114107712B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002027053A1 (en) * | 2000-09-26 | 2002-04-04 | Kwang Seon Shin | High strength magnesium alloy and its preparation method |
| CN101285144A (en) * | 2008-05-05 | 2008-10-15 | 哈尔滨工程大学 | Magnesium alloy for semi-solid forming and preparation method of semi- solid blank |
| CN101306464A (en) * | 2008-05-23 | 2008-11-19 | 北京科技大学 | Process for preparing high performance structural member with high SiC grain volume fraction |
| CN101403063A (en) * | 2008-11-26 | 2009-04-08 | 南昌大学 | Process for producing in situ AM60 magnesium-base composite material semi-solid state |
| CN101514409A (en) * | 2009-03-31 | 2009-08-26 | 南昌大学 | A method for preparing in situ MgSi particle reinforced metal matrix composite |
| CN101979697A (en) * | 2010-11-19 | 2011-02-23 | 江苏大学 | Method for preparing Mg2Si particle-reinforced bulk magnesium-based amorphous alloy composite material |
| CN111534731A (en) * | 2020-05-25 | 2020-08-14 | 珠海中科先进技术研究院有限公司 | Particle-reinforced medical magnesium-based composite material semi-solid billet and preparation method thereof |
| CN112746194A (en) * | 2020-10-29 | 2021-05-04 | 哈尔滨理工大学 | Al (aluminum)2O3Method for particle reinforced magnesium-based composite material and application thereof |
| CN113231791A (en) * | 2021-03-23 | 2021-08-10 | 北京交通大学 | Magnesium-based composite material cylinder sleeve for motorcycle engine and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 中国锻压协会编: "《特种锻造》", 31 May 2011, 北京：国防工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433862A (en) * | 2022-08-05 | 2022-12-06 | 太原理工大学 | Preparation method of Ni-free degradable magnesium-based material |
| CN115852223A (en) * | 2022-11-30 | 2023-03-28 | 西北有色金属研究院 | Preparation method of low-cost large-size ultrafine-grained biomedical magnesium-based composite material |
| CN115852223B (en) * | 2022-11-30 | 2024-01-26 | 西北有色金属研究院 | Preparation method of low-cost large-size ultrafine-grain biomedical magnesium-based composite material |
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