CN111331128A - Method for preparing zinc alloy degradable material by sintering metal powder - Google Patents
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Abstract
The invention provides a method for preparing a zinc alloy degradable material by sintering metal powder, which comprises the following steps: selecting zinc powder and metal element powder; putting zinc powder and metal element powder into a mixing tank, and mixing on a mixer; putting the mixed powder into a planetary high-energy ball mill for ball milling; pressing and sintering the mixed powder subjected to ball milling; after sintering, cooling the mixed powder blank to room temperature, removing pressure, and breaking vacuum and argon protection to obtain a sintered zinc alloy product; annealing and forging a zinc alloy sample; and rolling or extruding the forged zinc alloy to obtain a zinc alloy sheet or bar. The invention adopts the powder metallurgy preparation technology, can effectively solve the difference of the melting points of the alloy elements, can accurately control the proportion of each element in the alloy, and can obtain the zinc alloy material with low oxygen content, good quality, stable manufacturing method and realize batch production.
Description
Technical Field
The invention relates to the technical field of new biomedical materials and new powder metallurgy processing, in particular to a method for preparing a zinc alloy degradable material by sintering metal powder.
Background
After the degradable biomedical material is in service in an animal body fluid environment, the degradable biomedical material can be degraded, so that the lifelong problems caused by permanent implantation, such as long-term endothelial dysfunction, permanent physical stimulation, chronic inflammation local reaction and the like, are reduced or avoided. Elements in the common degradable metal medical material can be discharged in the metabolism process of the body, do not bring harm to tissues or organs, and are preferably functional elements which are necessary for the human body or can promote the healing of the tissues; meanwhile, the degradable metal medical material also has a proper degradation rate, so that the material can still maintain a sufficient mechanical supporting effect during service. At present, magnesium-based, iron-based and zinc-based alloys in metal materials are often developed as medical degradable metal materials due to good comprehensive mechanical properties and degradability.
Zinc has good biodegradability and tissue regeneration adaptability, is one of important essential elements of human body, plays a vital role in proliferation and differentiation of cells, and participates in regulation of immune system and nervous system of human body, promotes growth of human body and heals wound. The zinc can be used as a degradable bone implant material and a cardiovascular stent material and has proper biocompatibility and biodegradation rate. Pure zinc has poor mechanical properties, the yield strength of the pure zinc is less than 120MPa, and the pure zinc cannot meet the performance requirement that the pure zinc is used as a medical implant material and the strength of the pure zinc is more than 200MPa, so that the mechanical properties of zinc alloy are improved by adding alloy elements into zinc, and the aim of matching the mechanical properties with the degradation performance is fulfilled. Alloy elements added into zinc also have good biocompatibility and degradability, so that the mechanical property of the zinc alloy can be effectively improved, the biocompatibility is met, the degradation in body fluid is realized, and typical alloy elements which can be added include iron, magnesium, calcium and other alloy elements beneficial to a human body. However, when preparing binary or multi-element alloys of zinc, iron, magnesium and calcium, the main problem is that the melting point of zinc itself is the lowest, which is only 419.6 ℃, while the melting point of iron is 1535 ℃, the melting point of magnesium is 648.8 ℃ and the melting point of calcium is 839 ℃, so when preparing these alloy elements by smelting, the temperature of molten zinc liquid needs to be raised to be higher to melt these alloy elements, which easily causes the oxidation burning loss of zinc itself at high temperature. Even if the vacuum melting protection is adopted, the melting points of iron and calcium are too high, so that the iron and calcium are difficult to be fully melted to form zinc alloy with required content, and the problems of inaccurate zinc alloy components, more alloy melting casting defects and poor zinc alloy ingot casting quality after casting are caused.
Therefore, it is necessary to provide a method for preparing a zinc alloy material, which can effectively solve the difference of melting points of alloy elements, can accurately control the proportion of each element in the alloy, and can obtain a zinc alloy material with low oxygen content, stable and excellent quality and realize batch production.
Disclosure of Invention
The invention provides a method for preparing a zinc alloy degradable material by sintering metal powder, and aims to solve the problems of large melting point difference of alloy elements and inaccurate element proportion in the prior art.
In order to achieve the above object, the present invention provides a method for preparing a zinc alloy degradable material by sintering metal powder, comprising the steps of:
step 1, selecting zinc powder and metal element powder;
the granularity of the zinc powder and the metal element powder is 10-50 mu m, and the purity of the zinc powder and the metal element powder is more than 99.9%;
step 2, putting the zinc powder and the metal element powder selected in the step 1 into a material mixing tank capable of being sealed and filled with argon, and mixing the materials on a material mixing machine for 40-60 min;
step 3, putting the mixed powder obtained in the step 2 into a planetary high-energy ball mill for ball milling, wherein the ball milling time is adjusted according to the type of the mixed powder, and the ball-material ratio is 10: 1;
step 4, pressing the mixed powder subjected to ball milling in the step 3, placing the mixed powder blank obtained after pressing and forming in a vacuum hot pressing sintering furnace under the protection of argon, and simultaneously heating and pressurizing for sintering; the pressing pressure is 10MPa to 50 MPa;
step 5, after sintering, cooling the mixed powder blank to room temperature, removing pressure, and breaking vacuum and argon protection to obtain a sintered zinc alloy product;
step 6, annealing and forging the zinc alloy sample obtained in the step 5;
the annealing temperature is 100-200 ℃, the time is 4-24 h, and the annealing is finished and then the temperature is cooled to the room temperature; the forging temperature is between room temperature and 200 ℃, and the plastic deformation amount of the forging is 30-50%;
step 7, rolling or extruding the zinc alloy forged in the step 6 to obtain an aluminum alloy sheet or bar;
the rolling temperature is between room temperature and 200 ℃; the rolling can be carried out for multiple times, and the rolling deformation of each pass is 0-10%;
the extrusion temperature is 100-200 ℃, the extrusion ratio is more than 4, and the diameter of the obtained bar is 3-10 mm.
Preferably, the metal element powder in step 1 is one of iron powder, magnesium powder and calcium powder.
Preferably, in the step 2, when the metal element powder is iron powder, the mass ratio of the zinc powder to the metal element powder is Zn-0.1-10% Fe; when the metal element powder is magnesium powder, the mass ratio of the zinc powder to the metal element powder is Zn-0.1-10% of Mg; when the metal element powder is calcium powder, the mass ratio of the zinc powder to the metal element powder is Zn-0.1-10% of Ca; when more than one metal element powder is used, the addition amount of each element powder is in the range of 0.1-10%, such as Zn-0.1-10% Fe-0.1-10% Mg alloy composition.
Preferably, in the step 3, when the metal element powder is iron powder, the ball milling time is 4-24 hours; when the metal element powder is magnesium powder, the ball milling time is 2-12 h; when the metal element powder is calcium powder, the ball milling time is 1-6 h; when multiple element powders are put together for ball milling, the ball milling time is 1-24 h.
Preferably, the sintering operation in the step 4 is as follows: heating the formed mixed powder blank from the normal temperature to 360 ℃, preserving the heat for 10-20 min, continuously heating to the sintering temperature, and sintering for 10-60 min; the heating rate is 10-30 ℃/min; the sintering temperature is 450-1200 ℃; in the heating and sintering process, the pressure is 10 MPa-50 MPa.
Preferably, the specific operation of relieving the pressure in the step 5 is as follows: the pressure is gradually reduced during the cooling process, and when the temperature is less than 60 ℃, the pressure is completely relieved.
Preferably, in the step 7, annealing treatment is further performed at a temperature of 100-200 ℃ for 30-60 min in the middle of each rolling, and the total plastic deformation between two annealing treatments is less than 50%.
Preferably, in the step 7, the rod may be drawn on a drawing machine, the pass deformation is controlled within 10%, and the diameter of the obtained wire rod is more than 0.5 mm.
According to the invention, a zinc-iron, zinc-magnesium and zinc-calcium binary alloy or a multi-element alloy thereof is designed according to the requirements of mechanics and biocompatibility of a biomedical degradable zinc alloy material, the defect that the added iron, magnesium and calcium elements are difficult to accurately melt to form the zinc alloy due to low melting point of zinc is overcome, and the preparation method of the alloy is realized through a powder sintering technology, and in the ball milling process in the step 3, the X-Ray result of the alloy powder after ball milling can be analyzed through experiments according to the content of the added elements to finally obtain the optimized element powder ball milling time; in the pressing process of the step 4, according to different properties of the powder, such as granularity, proportion and the like, the pressing pressure can be adjusted to be increased or decreased, and the forming of the metal powder blank is realized.
The scheme of the invention has the following beneficial effects:
1. the addition of elements with different contents in a zinc matrix can be realized through the processes of ball milling, pressing and sintering of powder, particularly the addition of elements such as iron, calcium, magnesium and the like with a melting point greatly different from that of the zinc matrix, and the addition of the elements in a zinc melt with a low melting point is difficult to realize by adopting a conventional smelting and casting technology;
2. different metal elements can be accurately added by the powder metallurgy method, and especially when several elements are added simultaneously, the stability of alloy components can be guaranteed by the precision of powder metallurgy weighing and preparation processes;
3. the sintering process can well hinder the oxidation of the alloy under the protection of argon, and meanwhile, the temperature and the pressure in the sintering process can be accurately controlled, so that the alloys with different properties under different process conditions can be obtained, and the degradation performance of the alloy can be accurately regulated and controlled;
4. the sintered material after powder metallurgy can be made into a sheet by rolling, and also can be extruded and drawn to obtain a filament, so that the sintered material has good subsequent processing performance;
5. the powder metallurgy sintering technology is used for preparing the degradable zinc alloy material, the process flow is short, the control of the material components, the performance and the structural technical parameters is accurate, the product quality is stable, the production cost is low, and the method is suitable for batch production.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a microstructure diagram of a Zn-0.5% Fe alloy ingot of example 1;
FIG. 3 is a microstructure view of a rolled sheet of Zn-0.5% Fe alloy of example 1;
FIG. 4 is a microstructure diagram of a Zn-0.5% Mg alloy ingot of example 2;
FIG. 5 is a microstructure diagram of a Zn-1% Fe-1% Mg alloy ingot of example 3.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
Aiming at the existing problems, the invention provides a method for preparing a zinc alloy degradable material by sintering metal powder
Example 1
1, selecting zinc powder and iron powder with proper granularity, wherein the granularity of the zinc powder is between 10 and 20 mu m, the granularity of the iron powder is between 20 and 50 mu m, and the purity of the powder is over 99.9 percent;
step 2, weighing zinc powder and iron powder which are Zn-0.5% of Fe alloy components in mass ratio on an electronic balance, putting the weighed zinc powder and iron powder into a material mixing tank which can be sealed and filled with argon, and mixing the materials on a three-dimensional material mixer for 40 min;
step 3, putting the mixed metal powder into a planetary high-energy ball mill for ball milling, wherein the ball-material ratio is 10: 1, and the ball milling time is 4 hours;
step 4, placing the ball-milled zinc powder and iron powder in a mold, and pressing tightly under a cold press at the pressing pressure of 10 MPa; placing the pressed and formed metal powder in a vacuum hot-pressing sintering furnace with argon protection for sintering, heating to 360 ℃ from normal temperature, preserving heat for 10min, then heating to sintering temperature, wherein the sintering temperature is 1200 ℃, the sintering time is 10min, the heating rate is 10 ℃ per minute, and continuously keeping the pressure at 10MPa in the heating and sintering processes;
step 5, cooling after sintering is finished, wherein in the cooling process, the pressure is gradually reduced until the temperature is cooled to be below 60 ℃, the pressure is removed, the vacuum and argon protection are broken, and the die is taken out to obtain a sintered zinc-iron alloy product;
step 6, annealing treatment is carried out according to the sintered zinc-iron alloy sample, annealing is carried out for 4 hours at the temperature of 100 ℃, cooling is slowly carried out to the room temperature, the microstructure of the obtained sintered alloy blank is shown in figure 1, the annealed sample is forged at the room temperature, and the plastic deformation of forging is controlled to be 30 percent under the condition that no crack is generated;
and 7, rolling the forged zinc alloy at room temperature, controlling the rolling deformation of each pass to be within 10%, carrying out annealing treatment at 100 ℃ for 30min during rolling, and ensuring that the total plastic deformation between two annealing treatments is not more than 50%. After rolling, a sheet of zinc alloy having a thickness of 0.1mm was obtained, as shown in FIG. 1, and its microstructure as shown in FIG. 2.
Example 2
Step 1, selecting zinc powder and magnesium powder with proper particle sizes, wherein the particle size of the zinc powder is 40-50 mu m, the particle size of the magnesium powder is 40-50 mu m, and the purity of the powder is more than 99.9%;
step 2, mixing zinc powder and magnesium powder, weighing the mixture on an electronic balance according to Zn-0.5% of Mg alloy components, putting the mixture into a material mixing tank which can be sealed and filled with argon, and mixing the materials on a three-dimensional material mixer for 60 min;
step 3, putting the mixed metal powder into a planetary high-energy ball mill for ball milling, wherein the ball-material ratio is 10: 1, and the ball milling time is 12 hours;
step 4, placing the ball-milled metal powder in a die, and pressing tightly under a cold press at 50 MPa; placing the pressed and formed metal powder in a vacuum hot-pressing sintering furnace with argon protection, heating to 360 ℃ from normal temperature, preserving heat for 20min, then heating to the sintering temperature, wherein the sintering temperature is 450 ℃, the sintering time is 60min, the heating rate is 30 ℃ per minute, and continuously keeping the pressure at 50MPa in the heating and sintering processes;
and 5, cooling after sintering is finished, gradually reducing the pressure in the cooling process until the pressure is cooled to below 60 ℃, removing the pressure, breaking vacuum and argon protection, and taking out the die to obtain a sintered zinc-magnesium alloy product.
Step 6, annealing treatment is carried out according to the sintered zinc-magnesium alloy sample, annealing is carried out for 24 hours at the temperature of 200 ℃, cooling is slowly carried out to the room temperature, the microstructure of the obtained sintered alloy blank is shown in figure 3, the annealed sample is forged, the forging is carried out at the temperature of 200 ℃, the plastic deformation amount of the forging is controlled at 50 percent, and no crack is generated;
and 7, extruding the forged zinc-magnesium alloy at the extrusion temperature of 200 ℃ and the extrusion ratio of 8 to obtain a bar with the diameter of 3mm, drawing the bar on a wire drawing machine, and controlling the pass deformation within 10% to obtain wires with different diameters of more than 0.5 mm.
Example 3
1, selecting zinc powder, iron powder and magnesium powder with proper granularity, wherein the granularity of the powder is 20-30 mu m, and the purity of the powder is more than 99.9%;
step 2, weighing zinc powder, iron powder and magnesium powder on an electronic balance according to the designed alloy components Zn-1% Fe-1% Mg, placing the weighed zinc powder, iron powder and magnesium powder into a material mixing tank which can be sealed and filled with argon, and mixing the materials on a three-dimensional material mixing machine for 60 min;
step 3, putting the mixed metal powder into a planetary high-energy ball mill for ball milling, wherein the ball-material ratio is generally 10: 1, and the ball milling time is 24 hours;
step 4, placing the ball-milled metal powder in a mold, pressing tightly under a cold press at a pressing pressure of 40MPa, heating the pressed and formed metal powder from normal temperature to 360 ℃, preserving heat for 15min, then heating to a sintering temperature of 1000 ℃, sintering for 30min at a heating rate of 20 ℃ per minute, and continuously keeping the pressure at 30MPa in the heating and sintering processes;
step 5, cooling after sintering is finished, gradually reducing pressure in the cooling process until the pressure is cooled to be below 60 ℃, unloading the pressure, breaking vacuum and argon protection, and taking out a mold to obtain a sintered zinc-iron-magnesium alloy product;
step 6, annealing the sintered zinc alloy sample, annealing at 150 ℃ for 12h, slowly cooling to room temperature to obtain a sintered alloy blank microstructure as shown in fig. 4, forging the annealed sample at 100 ℃, and controlling the plastic deformation of the forging at 40% on the basis of no crack generation;
and 7, rolling the forged zinc alloy at 100 ℃, controlling the rolling deformation of each pass to be within 10%, carrying out annealing treatment at 200 ℃ for 60min in the middle of rolling, and ensuring that the total plastic deformation between two annealing treatments is not more than 50%. After rolling, the thinnest sheet thickness of the zinc-iron-magnesium alloy sheet was obtained and was 0.1 mm.
Example 4
1, selecting zinc powder and calcium powder with proper particle size, wherein the particle size of the powder is between 40 and 50 mu m, and the purity of the powder is more than 99.9 percent;
step 2, weighing zinc powder and calcium powder which comprise Zn-10% Ca by mass on an electronic balance, putting the weighed zinc powder and calcium powder into a material mixing tank which can be sealed and filled with argon, and mixing the materials on a three-dimensional material mixing machine for 60 min;
step 3, putting the mixed metal powder into a planetary high-energy ball mill for ball milling, wherein the ball-material ratio is 10: 1, and the ball milling time is 6 hours;
step 4, placing the ball-milled metal powder in a mold, pressing tightly under a cold press at a pressing pressure of 20MPa, placing the pressed and formed metal powder in a vacuum hot-pressing sintering furnace under the protection of argon, heating and pressurizing a metal powder blank, heating from normal temperature to 360 ℃ at a heating rate of 30 ℃ per minute, keeping the temperature for 20min, heating to a sintering temperature of 600 ℃, and sintering for 60min, wherein in the heating and sintering process, the pressure is continuously kept at 40 MPa;
and 5, cooling after sintering is finished, gradually reducing the pressure in the cooling process until the pressure is cooled to below 60 ℃, removing the pressure, breaking vacuum and argon protection, and taking out the die to obtain a sintered zinc-calcium alloy product.
Step 6, annealing the sintered zinc-calcium alloy sample, annealing at 100 ℃ for 4h, slowly cooling to room temperature, forging the annealed sample, and performing forging at room temperature, wherein the plastic deformation of the forging is controlled to be 40% under the condition that no crack is generated;
and 7, extruding the forged zinc alloy at the extrusion temperature of 100 ℃ and the extrusion ratio of more than 4 to obtain a bar with the diameter of 10mm, drawing the obtained bar on a wire drawing machine, and controlling the pass deformation within 10% to obtain wires with different diameters of more than 0.5 mm.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A method for preparing a zinc alloy degradable material by sintering metal powder is characterized by comprising the following steps:
step 1, selecting zinc powder and metal element powder;
the granularity of the zinc powder and the metal element powder is 10-50 mu m, and the purity of the zinc powder and the metal element powder is more than 99.9%;
step 2, putting the zinc powder and the metal element powder selected in the step 1 into a material mixing tank capable of being sealed and filled with argon, and mixing the materials on a material mixing machine for 40-60 min;
step 3, putting the mixed powder obtained in the step 2 into a planetary high-energy ball mill for ball milling, wherein the ball milling time is adjusted according to the type of the mixed powder, and the ball-material ratio is 10: 1;
step 4, pressing the mixed powder subjected to ball milling in the step 3, placing the mixed powder blank obtained after pressing and forming in a vacuum hot pressing sintering furnace under the protection of argon, and simultaneously heating and pressurizing for sintering; the pressing pressure is 10MPa to 50 MPa;
step 5, after sintering, cooling the mixed powder blank to room temperature, removing pressure, and breaking vacuum and argon protection to obtain a sintered zinc alloy product;
step 6, annealing and forging the zinc alloy sample obtained in the step 4;
the annealing temperature is 100-200 ℃, the time is 4-24 h, and the annealing is finished and then the temperature is cooled to the room temperature; the forging temperature is between room temperature and 200 ℃, and the plastic deformation amount of the forging is 30-50%;
step 7, rolling or extruding the zinc alloy forged in the step 6 to obtain a zinc alloy sheet or bar;
the rolling temperature is between room temperature and 200 ℃; the rolling can be carried out for multiple times, and the rolling deformation of each pass is 0-10%;
the extrusion temperature is 100-200 ℃, the extrusion ratio is more than 4, and the diameter of the obtained bar is 3-10 mm.
2. The method for preparing the zinc alloy degradable material by metal powder sintering according to the claim 1, wherein the metal element powder in the step 1 is one or more of iron powder, magnesium powder and calcium powder.
3. The method for preparing the zinc alloy degradable material by metal powder sintering as claimed in claim 1, wherein in the step 2, when the metal element powder is iron powder, the mass ratio of the zinc powder to the metal element powder is Zn-0.1-10% Fe; when the metal element powder is magnesium powder, the mass ratio of the zinc powder to the metal element powder is Zn-0.1-10% of Mg; when the metal element powder is calcium powder, the mass ratio of the zinc powder to the metal element powder is Zn-0.1-10% of Ca; when more than one metal element powder is used, the addition amount of each element powder is in the range of 0.1-10%.
4. The method for preparing the zinc alloy degradable material through metal powder sintering according to claim 1, wherein in the step 3, when the metal element powder is iron powder, the ball milling time is 4-24 h; when the metal element powder is magnesium powder, the ball milling time is 2-12 h; when the metal element powder is calcium powder, the ball milling time is 1-6 h; when more than one metal element powder is used, the ball milling time is 1-24 h.
5. The method for preparing the zinc alloy degradable material by metal powder sintering according to the claim 1 is characterized in that the specific operation of sintering in the step 4 is as follows: heating the formed mixed powder blank from the normal temperature to 360 ℃, preserving the heat for 10-20 min, continuously heating to the sintering temperature, and sintering for 10-60 min; the heating rate is 10-30 ℃/min; the sintering temperature is 450-1200 ℃; in the heating and sintering process, the pressure is 10 MPa-50 MPa.
6. The method for preparing the zinc alloy degradable material by metal powder sintering according to the claim 1, wherein the specific operation of relieving the pressure in the step 5 is as follows: the pressure is gradually reduced during the cooling process, and when the temperature is less than 60 ℃, the pressure is completely relieved.
7. The method for preparing the zinc alloy degradable material through metal powder sintering according to claim 1, wherein during the rolling in the step 7, annealing treatment is further performed at a temperature of 100-200 ℃ for 30-60 min in the middle of each rolling, and the total rolling deformation between the two annealing treatments is less than 50%.
8. The method for preparing the zinc alloy degradable material through metal powder sintering as claimed in claim 1, wherein the rod obtained by extrusion in the step 7 is subjected to drawing treatment on a wire drawing machine, the pass deformation is controlled within 10%, and the diameter of the obtained wire is more than 0.5 mm.
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| CN202010298541.2A CN111331128A (en) | 2020-04-16 | 2020-04-16 | Method for preparing zinc alloy degradable material by sintering metal powder |
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| CN202010298541.2A CN111331128A (en) | 2020-04-16 | 2020-04-16 | Method for preparing zinc alloy degradable material by sintering metal powder |
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