CN113322403A - Novel degradable high-toughness magnesium alloy bone nail material and preparation method thereof - Google Patents
Novel degradable high-toughness magnesium alloy bone nail material and preparation method thereof Download PDFInfo
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- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
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Abstract
The invention discloses a novel degradable high-toughness magnesium alloy bone nail material which comprises the following components in percentage by weight: zn: 0.01-1.5%; y: 1.2-5.5%; 1.8 to 2.6 percent of Nd; 0.01 to 0.5 percent of Zr; 0.3 to 1.5 percent of Mn; the balance being Mg. The invention firstThe magnesium alloy bone nail material is produced by adopting the groove rolling technology, the production feasibility is high, the efficiency is good, and the product is stable. The magnesium alloy bone nail material produced by the method has yield strength of 290-310 MPa, tensile strength of 320-350 MPa, elongation of 11-15%, and corrosion potential and corrosion current density of-1.6145V and 7.28 multiplied by 10 respectively‑6 A/cm2. The magnesium alloy bone nail material keeps excellent plasticity and corrosion performance under the condition of high strength.
Description
Technical Field
The invention belongs to the technical field of bone nail material preparation, and particularly relates to a novel degradable high-toughness magnesium alloy bone nail material and a preparation method thereof.
Background
Magnesium alloys are the lightest metals of construction materials and have densities of about 1/4 for steel and 2/3 for aluminum alloys. Through the development of magnesium alloys to manufacture and replace certain active components, the weight of the entire structure can be greatly reduced. In addition, the magnesium alloy has the following characteristics: (1) can be degraded in vivo, and the degradation product can be absorbed by human body or discharged from human body. (2) Promoting bone growth. The magnesium ions can promote the calcium deposition of human body in vivo, thereby promoting the growth of bone cells and improving the speed of bone healing. (3) No stress shielding effect. The magnesium alloy is a metal with the density and the elastic modulus which are most similar to those of human bones, has high specific strength, can provide a stable mechanical environment in the early stage of fracture healing, and has great advantages compared with stainless steel and titanium-based alloy on medical bone implant materials.
Currently, research, development and application of magnesium alloys mainly focus on overcoming the following two problems: (1) the corrosion resistance of the magnesium alloy in neutral and acid environments is not high; (2) the mechanical properties of magnesium alloy, such as strength and ductility, need to be further improved to meet various service requirements. The problem that how to solve the mechanical property of the magnesium alloy is needed to be solved when the magnesium alloy bone nail is popularized and applied is solved.
In 1878 Edward c. hue physicians were the first to be clinically successful in ligating blood vessels with magnesium wire, but magnesium was soon found to be highly brittle, mechanically poorly performing and degrading too rapidly, resulting in almost no research on magnesium and its alloys as medical implants. Due to the increasing activity of global research, many new high strength magnesium alloys have been produced through large plastic deformation and/or alloyed microstructure refinement. The MAGNEZIX magnesium alloy bone screw developed by German Syntellix company in 2013 has obtained European CE certification, and the product is widely applied to the treatment of thumb eversion at present, the bone screw is made of Mg-Y-Re-Zr alloy, the yield strength is more than 250 MPa, and the elongation is more than 10%. In 2021, Dyson et al produced Mg-Nd-Zn-Zr alloys having Ultimate Tensile Strength (UTS), Yield Strength (YS) and elongation of 312MPa, 308MPa and 12%, respectively, by an extrusion test, and the alloys were excellent in workability.
Alloying is one of the most common methods for improving the performance of magnesium alloy, the alloying elements of the magnesium alloy are various, at present, the Mg-Zn alloy and the Mg-Ca alloy are two biodegradable magnesium alloys which are widely researched, and both the Zn element and the Ca element are necessary elements for human bodies, and have the advantages of promoting bone repair, good cell compatibility and the like. However, the corrosion resistance of the magnesium alloy is enhanced by the two elements without being good by rare earth, so that the rare earth element is important for the alloying of magnesium. As for the rare earth elements, the addition of the rare earth elements can not only improve the mechanical property of the magnesium alloy, but also improve the corrosion resistance of the magnesium alloy. Such as rare earth Y, Gd, etc. can improve the corrosion resistance of the alloy, and Nd and Zr can refine the crystal grains of the magnesium alloy, thereby improving the strength and the corrosion uniformity of the alloy. It has been found that the addition of 0.2wt% of Mn element to magnesium alloys greatly changes the workability, such as extrudability, of the magnesium alloys. Further, Zhaoyongyou et al reported that a large amount of nano-scale α -manganese precipitates were formed in extruded Mg-1wt% Mn and Mg-3wt% Mn. Can inhibit the growth of crystal grains, thereby forming fine-grain magnesium alloy and obviously improving the mechanical property of the magnesium alloy. In addition, Mn is a necessary trace mineral element for human body, is an activator of various enzymes in human body, and can increase anticoagulation effect. Although a great deal of work tries to improve the comprehensive performance of the magnesium alloy bone nail by improving the processing technology and regulating the alloy components, the magnesium alloy bone nail has more or less defects, such as the mechanical property is reduced due to the over-high corrosion rate, and the service requirement cannot be met. Therefore, there is a need to develop new alloys and processing methods to produce bone screw materials that meet the service requirements.
Aiming at the background technology, the novel degradable high-toughness magnesium alloy bone nail material developed by the invention is a novel preparation technology, the as-cast alloy has good formability and processability, and a plurality of processing requirements of the magnesium alloy in the next step are met. Further, the high-strength biodegradable Mg-Zn-Y-Nd-Zr-Mn bone nail material with high strength and good plasticity is prepared by one-time extrusion and groove rolling.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel degradable high-toughness magnesium alloy bone nail material, which has the advantages of matching toughness and good corrosion resistance.
The invention also provides a preparation method of the novel degradable high-strength and toughness magnesium alloy bone nail material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel degradable high-toughness magnesium alloy bone nail material comprises the following components in percentage by weight:
zn: 0.01-1.5%; y: 1.2-5.5%; nd: 1.8-2.6%; zr: 0.01-0.5%; mn: 0.3-1.5%; the balance being Mg.
A large number of tests are carried out on the components of the magnesium alloy bone nail material, the Zr and Mn elements are selected and added according to the test verification result, the anticoagulation effect of the Mn element provides advantages for the material to be used as a bone implant material, and the Zr element greatly refines crystal grains and improves the mechanical property.
The invention also provides a preparation method of the novel degradable high-strength and high-toughness magnesium alloy bone nail material, which is used for producing the cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material, wherein Mg-30wt% of Y intermediate alloy is used as a Y raw material, Mg-30wt% of Nd intermediate alloy is used as an Nd raw material, Mg-30wt% of Zr intermediate alloy is used as a Zr raw material, Mg-30wt% of Mn intermediate alloy is used as a Mn raw material, and high-purity magnesium ingots and high-purity zinc ingots with the purity of more than or equal to 99.95 wt% are used as Mg and Zn raw materials.
The preparation method of the novel degradable high-strength and toughness magnesium alloy bone nail material specifically comprises the following operation steps:
(1) preparing materials: weighing high-purity magnesium ingots, high-purity zinc ingots, Mg-30wt% of Y intermediate alloy, Mg-30wt% of Nd intermediate alloy, Mg-30wt% of Zr intermediate alloy and Mg-30wt% of Mn intermediate alloy in corresponding mass in sequence according to the component proportion of the target Mg-Zn alloy; during the batching, the oil stain, sand, oxide, water and the like on the surfaces of raw materials and furnace materials are removed;
(2) pre-painting a crucible to prevent sand adhesion, then putting the crucible into a resistance furnace for heating, and introducing CO with the volume ratio of 99: 1 into the resistance furnace after the furnace temperature is increased to 350-500 DEG C2And SF6A protective gas;
(3) introducing protective gas for 10-20 min, adding high-purity magnesium ingots, heating to 700-730 ℃, and preserving heat until the magnesium ingots are completely melted;
(4) adding intermediate alloy of Y, Mg-30wt% of Mg and 30wt% of Nd and 30wt% of Mg, heating to 730-760 ℃, preserving heat until the intermediate alloy is completely melted, and uniformly stirring;
(5) adding Mg-30wt% of Mn intermediate alloy, preserving heat for 10-20 min, and uniformly stirring;
(6) putting a high-purity zinc ingot, and keeping the temperature for 10-20 min;
(7) refining the magnesium alloy liquid obtained in the step (6), and continuously scattering a refining agent on the surface of the magnesium alloy liquid at the same time until a bright mirror surface is observed on the surface of the magnesium alloy liquid; and then cooling to 700-730 ℃, stirring, slagging off, standing for 45-90 min, and then casting and demolding to obtain the as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material.
Further, refining the magnesium alloy liquid at the temperature of 710-750 ℃, wherein the dosage of a refining agent is 1-1.5% of the weight of the magnesium alloy liquid, and the refining time lasts for 5-10 min. The refining agent is hexachloroethane.
Preferably, the as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material can be further prepared into an extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material, which specifically comprises the following steps: preserving the temperature of the extruded sample at 340-440 ℃ for 3-5h, taking out and putting the extruded sample into a die for extrusion, wherein the parameters of the extrusion process are as follows: the extrusion ratio is 5-20, and the extrusion rate is 0.5-1 mm/min. The extruded sample had a diameter of 90 mm.
Preferably, the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material can be further prepared into a rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material, which specifically comprises the following steps: a pass rolling mill is selected for rolling (the number of the rolls of the pass rolling mill used in the invention is 18 groups), and the diameter of a rolling groove between the rolls of the same group is 8-25 mm. The sizes of the rolling grooves of adjacent groups of rollers are reduced in sequence, and the reduction of each group is 1 mm; the roller moves at a linear speed of 150-300 mm/s.
Specifically, before rolling, the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material is annealed at 260-320 ℃ for 30-90 min, air-cooled (namely naturally cooled to room temperature in air), and then rolled in a rolling mill.
Furthermore, the sample passes through each group of rollers four times, the sample is rotated by 90 degrees clockwise relative to the previous rolling before each rolling (the sample is square, namely, each side is rolled to ensure uniformity), and the sample is immediately straightened after one group of rolling is finished.
Preferably, after each group of rolling is finished, annealing the sample at 200-260 ℃ for 30-60 min, and continuing to perform the next rolling after air cooling; the rolling is carried out for 1-4 times in total, and the final rolling diameter is 22-25 mm.
Compared with the prior magnesium alloy bone nail material, the invention has the following advantages:
the magnesium alloy bone nail material is produced by adopting a pass rolling method for the first time, the alloy components are reasonably designed, the added elements are all metal elements required by a human body, and the high-strength biodegradable bone-implanted Mg-Zn-Y-Nd-Zr-Mn bone nail material with high toughness matching and good corrosion resistance is produced by smelting, extruding and pass rolling methods; the method has the advantages of short production time, simple operation, high efficiency and high product qualification rate. In addition, the yield strength of the magnesium alloy bone nail material produced by the method can reach 290-310 MPa, the tensile strength can reach 320-350 MPa, the elongation rate is 11-15%, and the corrosion potential and the corrosion current density respectively reach-1.6145V and 7.28 multiplied by 10-6 A/cm2And the corrosion current density is greatly reduced, so that the corrosion resistance is obviously improved. The magnesium alloy bone nail material of the invention still maintains excellent plasticity and corrosion resistance under the condition of high strength.
Drawings
FIG. 1 is a schematic diagram of the operation of a pass rolling mill used in the present invention;
FIG. 2 is a gold phase diagram of an as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 1;
FIG. 3 is a tensile curve of an as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 1;
FIG. 4 is a graph showing electrochemical corrosion tests of as-cast Mg-Zn-Y-Nd-Zr-Mn alloy nail materials prepared in example 1;
FIG. 5 is a gold phase diagram of an extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 2;
FIG. 6 is a tensile curve of an extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 2;
FIG. 7 is an electrochemical corrosion test chart of the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 2;
FIG. 8 is a gold phase diagram of a rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 3;
FIG. 9 is a tensile curve of a rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 3;
FIG. 10 is an electrochemical corrosion test chart of the rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 3.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, the purity of the high purity magnesium ingot and the high purity zinc ingot used was not less than 99.95 wt%, and the ordinary commercial products were directly purchased.
Example 1
A novel degradable high-toughness Mg-Zn-Y-Nd-Zr-Mn magnesium alloy bone nail material comprises the following components in percentage by weight: zn: 0.70 percent; y: 1.47%; nd: 1.93 percent; zr: 0.43 percent; mn: 0.6 percent; the balance being Mg.
The preparation method of the novel degradable high-toughness Mg-Zn-Y-Nd-Zr-Mn magnesium alloy bone nail material comprises the following steps:
(1) preparing materials: weighing 3000g of high-purity magnesium ingot, 26.69g of high-purity zinc ingot, 51.38g of Mg-30wt% Y intermediate alloy, 67.46g of Mg-30wt% Nd intermediate alloy, 15.03g of Mg-Zr30wt% intermediate alloy and 20.97g of Mg-30wt% Mn intermediate alloy according to the proportion, considering the burning loss rate of each element during smelting, preparing 20% of Zn element in excess and preparing 10% of Y, Nd, Zr and Mn element in excess. During the batching, the oil stain, sand, oxide, water and the like on the surfaces of raw materials and furnace materials are removed; the magnesium alloy in the embodiment comprises the following specific components: zn =0.70%, Y =1.47%, Nd =1.93%, Zr =0.43%, Mn =0.6%, and the balance of Mg and other unavoidable impurity elements, wherein Na is less than or equal to 0.07%, Si is less than or equal to 0.03%, AL is less than or equal to 0.03%, and K is less than or equal to 0.03%;
(2) smelting:
(a) pre-painting the crucible to prevent sand adhesion, then putting the crucible into a resistance furnace for heating, and introducing CO with the volume ratio of 99: 1 into the resistance furnace after the furnace temperature is raised to 400 DEG C2And SF6A protective gas;
(b) introducing protective gas for 15min, adding high-purity magnesium ingot, heating to 720 ℃, and keeping the temperature until the magnesium ingot is completely melted;
(c) adding intermediate alloy of Mg-30wt% Y, Mg-30wt% Nd and Mg-30wt% Zr, heating to 760 ℃, preserving heat until the intermediate alloy is completely melted, and uniformly stirring;
(d) adding Mg-30wt% of Mn intermediate alloy, keeping the temperature for 10min, and stirring uniformly;
(e) putting high-purity zinc ingot, keeping the temperature for 10min, and cooling to 740 ℃;
(3) refining: refining the magnesium alloy liquid obtained in the step (2), continuously scattering a refining agent (the amount of the refining agent is 1.2% of the weight of the magnesium alloy liquid, and the component of the refining agent is hexachloroethane) on the surface of the magnesium alloy liquid, refining at the temperature of 740 ℃ for 10min, and refining until a bright mirror surface is observed on the surface of the magnesium alloy liquid;
(4) then cooling to 720 ℃, stirring the refined magnesium alloy liquid, slagging off, preserving heat and standing for 60 min;
(5) casting: the preheated mold is removed from the oven and is ready for casting. Before pouring, introducing shielding gas (the volume ratio of the shielding gas to the CO is 99: 1)2And SF6Composition) for 4 minutes. Casting and demolding to obtain the as-cast Mg-Zn-Y-Nd-Zr-Mn alloy.
FIG. 2 is a gold phase diagram of an as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 1; the as-cast bone screw material is seen to have a uniform texture with a grain size of about 30 μm.
FIG. 3 is a drawing curve showing the tensile strength of an as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 1; as can be seen, the tensile strength of the as-cast bone screw material is about 175 MPa, and the elongation is about 12%.
FIG. 4 is a graph showing electrochemical corrosion tests of the as-cast Mg-Zn-Y-Nd-Zr-Mn alloy nail material prepared in example 1; the figure shows that the as-cast bone nail material has higher corrosion potential, lower corrosion current density and better corrosion resistance.
Example 2
The as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material obtained in example 1 was prepared into an extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material by the following operations:
1. preparation of experimental materials:
(a) an extruder (checking an extrusion barrel and a hydraulic cylinder), a die (checking whether the die is cleaned up or not by a die with the diameter of phi 30 mm), a die test is required before extrusion, and a heating furnace (checking the temperature of the furnace at 400 ℃) in advance);
(b) 1 industrial fan, and performing forced air cooling on the bar at an extrusion outlet;
(c) gloves for extrusion, clips, thermocouples, wire couples, lubricants (graphite).
2. The mold was heated and the mold temperature was raised to 420 ℃ using a thermocouple.
3. Preheating an extruded sample: adjusting the temperature of the heating furnace to 400 +/-5 ℃, putting an extrusion sample (the extrusion ratio is 9) with the diameter of 90mm, keeping the temperature for 4 hours, and then discharging the sample out of the furnace for extrusion.
4. The extrusion speed is 0.5mm/min, the extrusion is carried out at the lowest extrusion speed of the extruder, the adjustment can be carried out according to the actual situation, the continuous extrusion is carried out in the extrusion process, and the forced air cooling is carried out at the extrusion outlet.
And 5, straightening, and immediately straightening the extruded Mg-Zn-Y-Nd-Zr-Mn alloy after extrusion.
FIG. 5 shows a gold phase diagram of an extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 2; it can be seen that the extruded bone screw material has a uniform structure, fine grains and an average grain size of about 7 μm.
FIG. 6 is a drawing curve showing the tensile strength of the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 2; the figure shows that the extruded bone nail material has better plasticity, the elongation rate reaches 20 percent, and the tensile strength is greatly improved compared with the cast bone nail material.
FIG. 7 is a graph showing electrochemical corrosion tests of the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 2; it can be seen that the corrosion potential of the extruded bone screw material is reduced, the corrosion current density is increased, and the corrosion resistance is reduced.
Example 3
The extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material obtained in the example 2 is prepared into a rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material by the following operation:
1. annealing: and (3) annealing the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material (phi 30mm x 400 mm) at 300 ℃ for 80min, immediately taking out after the annealing is finished, and cooling in air.
2. Starting up: the upper roller and the lower roller of the hole type rolling mill (the working principle diagram is shown in figure 1) are respectively connected with the positive electrode and the negative electrode of a power supply, and the linear speeds of the upper roller and the lower roller are both 200 mm/s. The number of the rollers is 18 groups, and the diameter of the groove between the rollers in the same group is 25 mm. The sizes of the grooves of the adjacent groups of rollers are reduced in sequence, and the reduction of each group is 1 mm.
3, feeding: the air-cooled sample is fed into a rolling groove with the diameter of 25mm, after the sample passes through the rolling groove for one time, the sample is taken out immediately for the next rolling, the group of rollers passes through the rolling groove for four times in total, and before each rolling, the sample is rotated by 90 degrees clockwise relative to the previous sample feeding position and then is fed into the rolling groove with the diameter of 25 mm.
4. And (4) straightening, namely straightening the sample immediately after one group of rolling is finished.
5. And (3) intermediate annealing, annealing the sample in the step (4) at 260 ℃ for 30min, air cooling, and then continuing to perform next rolling, wherein the rolling mill pressing amount is increased by 1mm compared with that in the step (3). The rest of the operation is the same as step 3.
6. And (4) straightening, namely immediately straightening the sample after rolling is finished. The final rolling diameter is about 24 mm.
FIG. 8 is a gold phase diagram of a rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 3; it can be seen that the grains of the rolled bone screw material are greatly refined, and the grain size is about 4 μm.
FIG. 9 shows the tensile curve of the rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 3; the drawing shows that the tensile strength of the rolled bone nail material is greatly improved to be about 330MPa, and the implantation requirement of the medical bone nail material is met.
FIG. 10 is a graph showing the electrochemical corrosion test of the rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone screw material prepared in example 3; the figure shows that the corrosion potential of the rolled bone nail material is higher, the corrosion current density is higher, and the corrosion resistance is better.
Example 4
A novel degradable high-toughness magnesium alloy bone nail material comprises the following components in percentage by weight:
zn: 0.01-1.5%; y: 1.2-5.5%; 1.8-2.6% of Nd; 0.01-0.5% of Zr; 0.3-1.5% of Mn; the balance being Mg.
According to the embodiments 1, 2 and 3, the degradable high-strength and toughness magnesium alloy bone nail material in the casting state, the extrusion state and the rolling state is respectively prepared.
Example 5
A novel degradable high-toughness magnesium alloy bone nail is composed of the following components in percentage by weight:
zn: 0.01-1.5%; y: 1.2-5.5%; 1.8-2.6% of Nd; 0.01-0.5% of Zr; 0.3-1.5% of Mn; the balance being Mg.
According to the embodiments 1, 2 and 3, the degradable high-strength and toughness magnesium alloy bone nail material in the casting state, the extrusion state and the rolling state is respectively prepared.
Table 1 shows the mechanical properties of the Mg-Zn-Y-Nd-Zr-Mn bone screw material prepared in examples 1 to 3. As can be seen from the data of example 3 of table 1: the yield strength and the mechanical strength of the Mg-Zn-Y-Nd-Zr-Mn bone nail material prepared by the method are both more than 300MPa, and the elongation at break is more than 10%, which shows that the magnesium alloy bone nail material has high strength and good plasticity, and meets the service requirements of the magnesium alloy bone nail material on various occasions.
Table 1: mechanical properties of Mg-Zn-Y-Nd-Zr-Mn bone nail materials prepared in examples 1 to 3
Table 2 shows the corrosion properties of the Mg-Zn-Y-Nd-Zr-Mn bone screw materials prepared in examples 1 to 3. Wherein the self-corrosion potentials of the cast Mg-Zn-Y-Nd-Zr-Mn alloy, the extruded Mg-Zn-Y-Nd-Zr-Mn alloy and the rolled Mg-Zn-Y-Nd-Zr-Mn alloy are-1.6283V, -1.6591V and-1.6145V respectively; the corrosion current density is 8.55 multiplied by 10 respectively-6 A/cm2、9.36×10-6 A/cm2、7.28×10-6 A/cm2(see figures 4, 7 and 10 for details). The corrosion potential is increased, the corrosion current density is reduced, and the corrosion resistance is improved. The data in table 2 show that compared with other magnesium alloy bone nail materials, the corrosion current density of the Mg-Zn-Y-Nd-Zr-Mn bone nail material is greatly reduced, so that the corrosion resistance is remarkably improved.
Table 2: corrosion performance of Mg-Zn-Y-Nd-Zr-Mn bone nail materials prepared in examples 1 to 3
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. The novel degradable high-toughness magnesium alloy bone nail material is characterized by comprising the following components in percentage by weight:
zn: 0.01-1.5%; y: 1.2-5.5%; nd: 1.8-2.6%; zr: 0.01-0.5%; mn: 0.3-1.5%; the balance being Mg.
2. The preparation method of the novel degradable high-strength tough magnesium alloy bone nail material of claim 1 is characterized in that when producing an as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material, Mg-30wt% of Y intermediate alloy is used as a Y raw material, Mg-30wt% of Nd intermediate alloy is used as a Nd raw material, Mg-30wt% of Zr intermediate alloy is used as a Zr raw material, Mg-30wt% of Mn intermediate alloy is used as a Mn raw material, and high-purity magnesium ingots and high-purity zinc ingots with the purity of more than or equal to 99.95 wt% are used as Mg and Zn raw materials.
3. The preparation method of the novel degradable high-strength tough magnesium alloy bone nail material according to claim 2, which is characterized by comprising the following operation steps:
(1) preparing materials: weighing high-purity magnesium ingots, high-purity zinc ingots, Mg-30wt% of Y intermediate alloy, Mg-30wt% of Nd intermediate alloy, Mg-30wt% of Zr intermediate alloy and Mg-30wt% of Mn intermediate alloy in corresponding mass in sequence according to the proportion;
(2) heating the crucible in a resistance furnace, introducing CO at a volume ratio of 99: 1 into the resistance furnace after the furnace temperature is raised to 350-500 DEG C2And SF6A protective gas;
(3) introducing protective gas for 10-20 min, adding high-purity magnesium ingots, heating to 700-730 ℃, and preserving heat until the magnesium ingots are completely melted;
(4) adding intermediate alloy of Y, Mg-30wt% of Mg and 30wt% of Nd and 30wt% of Mg, heating to 730-760 ℃, preserving heat until the intermediate alloy is completely melted, and uniformly stirring;
(5) adding Mg-30wt% of Mn intermediate alloy, preserving heat for 10-20 min, and uniformly stirring;
(6) putting a high-purity zinc ingot, and keeping the temperature for 10-20 min;
(7) refining the magnesium alloy liquid obtained in the step (6), and continuously scattering a refining agent on the surface of the magnesium alloy liquid at the same time until a bright mirror surface is observed on the surface of the magnesium alloy liquid; and then cooling to 700-730 ℃, stirring, slagging off, standing for 45-90 min, and then casting and demolding to obtain the as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material.
4. The preparation method of the novel degradable high-strength and toughness magnesium alloy bone nail material according to claim 3, wherein the refining is carried out at a temperature of 710-750 ℃ of the temperature of the magnesium alloy liquid, the amount of the refining agent is 1-1.5% of the weight of the magnesium alloy liquid, and the refining time lasts for 5-10 min.
5. The preparation method of the novel degradable high-strength ductile magnesium alloy bone nail material according to claim 3, which is characterized in that the as-cast Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material is prepared into an extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material, and specifically comprises the following steps: preserving the temperature of the extruded sample at 340-440 ℃ for 3-5h, taking out and putting the extruded sample into a die for extrusion, wherein the parameters of the extrusion process are as follows: the extrusion ratio is 5-20, and the extrusion rate is 0.5-1 mm/min.
6. The preparation method of the novel degradable high-strength ductile magnesium alloy bone nail material according to claim 5, which is characterized in that the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material is prepared into a rolled Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material, and specifically comprises the following steps: rolling by using a hole type rolling mill, wherein the diameter of a rolling groove between the same group of rollers is 8-25 mm; the sizes of the rolling grooves of adjacent groups of rollers are reduced in sequence, and the reduction of each group is 1 mm; the roller moves at a linear speed of 150-300 mm/s.
7. The preparation method of the novel degradable high-strength tough magnesium alloy bone nail material according to claim 6, wherein before rolling, the extruded Mg-Zn-Y-Nd-Zr-Mn alloy bone nail material is annealed at 260-320 ℃ for 30-90 min, air-cooled and then fed into a rolling mill.
8. The preparation method of the novel degradable high-strength tough magnesium alloy bone nail material according to claim 7, wherein the sample passes through each group of rollers four times, the sample rotates clockwise 90 degrees relative to the last rolling before each rolling, and the sample is immediately straightened after one group of rolling is completed.
9. The preparation method of the novel degradable high-strength tough magnesium alloy bone nail material according to claim 8, wherein after each group of rolling is finished, the sample is annealed at 200-260 ℃ for 30-60 min, and then the next rolling is continued after air cooling; the rolling is carried out for 1-4 times in total, and the final rolling diameter is 22-25 mm.
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| CN114366271A (en) * | 2021-11-22 | 2022-04-19 | 奚廷斐 | Bone screw suitable for biological magnesium alloy and preparation method thereof |
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