阅读说明：本技术 医用锌合金丝材及其制备方法、应用 (Medical zinc alloy wire and preparation method and application thereof ) 是由 白晶 王子昕 程兆俊 邵怡 于 2020-12-30 设计创作，主要内容包括：本发明提一种医用锌合金丝材及其制备方法、应用,属于医用金属材料技术领域。其中,医用锌合金丝材的制备方法具体包括：将各合金组分进行熔炼,并经过浇注和冷却后得到锌合金铸锭；将锌合金铸锭经均匀化处理后热挤压以得到锌合金棒材；对所述锌合金棒材进行多道往复拉拔处理、分级退火处理,以获得所述医用锌合金丝材。本发明采用往复拉拔是一种新型拉拔方式,利用两种方向的往复拉拔加工处理,配合适当的变形量,使得材料在拉拔过程中短时间内受到两个不同方向的轴向力,二者会部分抵消,可以很大程度地削弱其在单向拉拔过程中产生的严重各向异性和成分偏析,从而改善了合金材料的内部组织形貌、力学性能以及腐蚀性能。(The invention provides a medical zinc alloy wire material, a preparation method and application thereof, and belongs to the technical field of medical metal materials. The preparation method of the medical zinc alloy wire specifically comprises the following steps: smelting the alloy components, and obtaining a zinc alloy ingot after pouring and cooling; homogenizing the zinc alloy cast ingot, and then carrying out hot extrusion to obtain a zinc alloy bar; and carrying out multi-channel reciprocating drawing treatment and graded annealing treatment on the zinc alloy bar to obtain the medical zinc alloy wire. The invention adopts the reciprocating drawing to be a novel drawing mode, utilizes the reciprocating drawing processing in two directions and is matched with proper deformation, so that the material is subjected to axial forces in two different directions within a short time in the drawing process, the axial forces and the axial forces can be partially offset, and the serious anisotropy and the component segregation generated in the unidirectional drawing process can be weakened to a great extent, thereby improving the internal structure appearance, the mechanical property and the corrosion property of the alloy material.)

1. A preparation method of medical zinc alloy wire is characterized by comprising the following steps: smelting the alloy components, and obtaining a zinc alloy ingot after pouring and cooling;

carrying out homogenization treatment on the zinc alloy cast ingot, and then carrying out hot extrusion to obtain a zinc alloy bar;

and carrying out multi-channel reciprocating drawing treatment and graded annealing treatment on the zinc alloy bar to obtain the medical zinc alloy wire.

2. The method of claim 1, wherein the steps of melting the alloy components, pouring and cooling to obtain the zinc alloy ingot comprise:

weighing required metal raw materials according to the mass percentage of alloy components, heating pure zinc to the temperature range of 420-470 ℃, introducing protective atmosphere after the pure zinc is completely melted, and heating to the temperature of 580-620 ℃; then adding the other weighed metal raw materials, stirring uniformly, standing for 20-40 min, stirring and standing for 8-12 min after the metal is completely melted, pouring when the temperature is reduced to 480-520 ℃, and air-cooling to room temperature to obtain the zinc alloy ingot.

3. The method of claim 2, wherein the zinc alloy ingot has a composition comprising up to 1 wt.% Li, 0 to 1 wt.% Mn, and/or 0 to 5 wt.% Cu, with the balance being Zn.

4. The method of claim 2, wherein the protective atmosphere is CO₂And SF₆The mixed gas of (1).

5. The method of claim 1, wherein the hot extrusion of the zinc alloy ingot after the homogenization treatment to obtain a zinc alloy bar comprises:

homogenizing the zinc alloy cast ingot under the conditions that the treatment temperature range is 220-270 ℃ and the heat preservation time range is 1-3 h;

and carrying out hot extrusion treatment on the homogenized zinc alloy cast ingot under the conditions that the extrusion temperature range is 130-230 ℃, the extrusion ratio range is 14-18 and the extrusion speed range is 1-3 mm/s, so as to obtain a zinc alloy bar with the diameter range of 2-3 mm.

6. The method of claim 1, wherein the subjecting the zinc alloy bar to a plurality of reciprocating drawing processes comprises:

the drawing direction of each pass of drawing processing on the zinc alloy bar is opposite to that of the previous pass; wherein the content of the first and second substances,

the deformation range of single pass is 5-25%, and the deformation of each pass of drawing treatment is increased in a gradient manner.

7. The method of claim 1, wherein the step anneal process comprises:

performing first-stage annealing treatment in an air environment, wherein the temperature range of the first-stage annealing treatment is 150-300 ℃, and the heat preservation time range is 10-30 min; and the number of the first and second groups,

and performing secondary annealing treatment in distilled water environment, wherein the temperature range of the secondary annealing treatment is 60-80 ℃, and the heat preservation time range is 8-12 min.

8. A method according to any one of claims 1 to 7, wherein the medical zinc alloy wire has a diameter in the range 0.1mm to 0.5 mm.

9. A medical zinc alloy wire produced by the method of any one of claims 1 to 8.

10. Use of a medical zinc alloy wire according to claim 9 in at least one of an anastomosis nail, an absorbable surgical suture, a vascular stent, an intestinal stent, a tracheal stent, and a urethral stent.

Technical Field

The invention belongs to the technical field of medical metal materials, and particularly relates to a medical zinc alloy wire, a preparation method of the medical zinc alloy wire and application of the medical zinc alloy wire.

Background

The wire compositions currently in use in the biomedical field are mainly titanium alloy, cobalt-nickel alloy and shape memory alloy, however, the above three materials have some problems, such as: titanium alloys have poor wear resistance, and the product of particles abraded after the surface oxide film is damaged may cause great harm to human body. In contrast, although cobalt-nickel alloys are excellent in corrosion resistance and wear resistance, medical materials prepared from cobalt-nickel alloys have a high loosening rate, and the precipitated Co and Ni elements have a problem of severe sensitization, and the cobalt-nickel alloys are expensive. In clinical application, if the surface of the alloy is not properly treated, the ion penetration into the periphery of the alloy can cause cell and tissue necrosis. In addition, the materials are all non-degradable inert metal materials, and when used as wires, the materials can only be remained in the body for a long time and cannot be taken out like orthopedic fixation materials through secondary operations, which further aggravates the negative effects of the materials.

Based on long-term experimental research, the inventor finds that the zinc alloy wire has excellent mechanical property, degradation property and biocompatibility, can be used as a good substitute of the materials to a certain extent, such as zinc-lithium alloy and the like, and has great potential in the field of biological medical treatment. The addition of other specific alloying elements to the zinc-lithium alloy may lead to materials with correspondingly more valuable properties, and therefore, more intensive research on the components of the zinc-lithium alloy is necessary.

On the other hand, the zinc alloy wire mentioned in the prior art is prepared mainly by a conventional unidirectional drawing method, and the method causes remarkable anisotropy and composition segregation in the alloy. The high anisotropy and the composition segregation phenomena can cause the phenomenon of nonuniform structure in the prepared alloy material, and the detected performance is as follows: the mechanical property, the corrosion resistance and the like are greatly influenced, which brings great inconvenience and limitation to future medical clinical application, and even no way is successfully applied to the actual life.

Therefore, based on the technical problems, the invention provides a novel preparation method of medical zinc alloy wire, zinc alloy wire and application thereof.

Disclosure of Invention

The invention aims to at least solve one of the technical problems in the prior art and provides a medical zinc alloy wire, a preparation method of the medical zinc alloy wire and application of the medical zinc alloy wire.

The invention provides a preparation method of a medical zinc alloy wire, which comprises the following specific steps: smelting the alloy components, and obtaining a zinc alloy ingot after pouring and cooling;

carrying out homogenization treatment on the zinc alloy cast ingot, and then carrying out hot extrusion to obtain a zinc alloy bar;

and carrying out multi-channel reciprocating drawing treatment and graded annealing treatment on the zinc alloy bar to obtain the medical zinc alloy wire.

Optionally, the smelting of each alloy component, and the casting and cooling to obtain a zinc alloy ingot casting include:

weighing required metal raw materials according to the mass percentage of alloy components, heating pure zinc to the temperature range of 420-470 ℃, introducing protective atmosphere after the pure zinc is completely melted, and heating to the temperature of 580-620 ℃; then adding other weighed metal raw materials, stirring uniformly, standing for 20-40 min, stirring and standing for 8-12 min after the metal is completely melted, pouring when the temperature is reduced to 480-520 ℃, and air-cooling to room temperature to obtain the zinc alloy ingot.

Optionally, the components of the zinc alloy ingot include less than 1 wt.% of Li, 0-1 wt.% of Mn and/or 0-5 wt.% of Cu, and the balance being Zn.

Optionally, theThe protective atmosphere is CO₂And SF₆The mixed gas of (1).

Optionally, the hot extrusion after the homogenization treatment of the zinc alloy ingot to obtain a zinc alloy bar includes:

homogenizing the zinc alloy cast ingot under the conditions that the treatment temperature range is 220-270 ℃ and the heat preservation time range is 1-3 h;

and carrying out hot extrusion treatment on the homogenized zinc alloy cast ingot under the conditions that the extrusion temperature range is 130-230 ℃, the extrusion ratio range is 14-18 and the extrusion speed range is 1-3 mm/s, so as to obtain a zinc alloy bar with the diameter range of 2-3 mm.

Optionally, the performing a plurality of reciprocating drawing processes on the zinc alloy bar includes:

the drawing direction of each pass of drawing processing on the zinc alloy bar is opposite to that of the previous pass; wherein the content of the first and second substances,

the deformation range of single pass is 5-25%, and the deformation of each pass of drawing treatment is increased in a gradient manner.

Optionally, the step annealing includes:

performing first-stage annealing treatment in an air environment, wherein the temperature range of the first-stage annealing treatment is 150-300 ℃, and the heat preservation time range is 10-30 min; and the number of the first and second groups,

and performing secondary annealing treatment in distilled water environment, wherein the temperature range of the secondary annealing treatment is 60-80 ℃, and the heat preservation time range is 8-12 min.

Optionally, the diameter range of the medical zinc alloy wire is 0.1 mm-0.5 mm.

In another aspect of the invention, a medical zinc alloy wire is provided, which is prepared by the method described above.

In another aspect of the present invention, an application of the medical zinc alloy wire is provided, and the medical zinc alloy wire described above can be applied to at least one of an anastomosis nail, an absorbable surgical suture, a vascular stent, an intestinal stent, a tracheal stent and a urethral stent.

The invention provides a preparation method of a medical zinc alloy wire, which comprises the following specific steps: smelting the alloy components, and obtaining a zinc alloy ingot after pouring and cooling; carrying out homogenization treatment on the zinc alloy cast ingot, and then carrying out hot extrusion to obtain a zinc alloy bar; and carrying out multi-channel reciprocating drawing treatment and graded annealing treatment on the zinc alloy bar to obtain the medical zinc alloy wire. The invention adopts the reciprocating drawing to be a novel drawing mode, utilizes the reciprocating drawing processing in two directions and is matched with proper deformation, so that the material is subjected to axial forces in two different directions within a short time in the drawing process, the axial forces and the axial forces can be partially offset, and the serious anisotropy and the component segregation generated in the unidirectional drawing process can be weakened to a great extent, thereby improving the internal structure appearance, the mechanical property and the corrosion property of the alloy material. Secondly, the processing technology of graded annealing is adopted, the texture structure and distribution of the zinc alloy wire are more uniform by the graded annealing and the rapid cooling, and the stress action and the component segregation hazards caused by extrusion and drawing in the wire are effectively removed. In addition, the treatment and heat preservation time required in the whole grading annealing process is shorter than that of the traditional heat treatment, so that the preparation efficiency and the preparation cost of the zinc alloy wire are greatly improved.

Drawings

FIG. 1 is a flow chart of a method for manufacturing a medical zinc alloy wire according to an embodiment of the invention;

FIG. 2 is a schematic view of a zinc alloy rod in the process of manufacturing a medical zinc alloy wire according to another embodiment of the present invention;

FIG. 3 is a schematic view showing the stress condition in the reciprocating drawing process in the preparation process of a medical zinc alloy wire according to another embodiment of the present invention;

FIG. 4 is a schematic view of a medical zinc alloy wire according to another embodiment of the present invention.

Detailed Description

In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.

As shown in FIG. 1, in one aspect of the present invention, a method S100 for preparing a medical zinc alloy wire is provided, which specifically includes the following steps S110 to S130:

and S110, smelting the alloy components, and pouring and cooling to obtain a zinc alloy ingot.

Specifically, required metal raw materials (such as Zn, Li, Mn and Cu) are weighed according to the mass percentage of alloy components for smelting, firstly, pure zinc is heated to the temperature range of 420-470 ℃, protective atmosphere is introduced after pure zinc is completely molten, and the temperature is raised to 580-620 ℃; then adding the other weighed metal raw materials, stirring uniformly, standing for 20-40 min, stirring and standing for 8-12 min after the metal is completely melted, pouring when the temperature is reduced to 480-520 ℃, and air-cooling to room temperature to obtain the zinc alloy ingot.

It should be noted that, based on long-term experimental research by the inventor, it is found that the zinc alloy wire has excellent mechanical properties, degradation properties and biocompatibility, and the Mn element can greatly optimize the strength and plasticity of the zinc alloy wire without affecting the cellular compatibility of the material, and maintain the stability of the strength, so as to ensure that the produced anastomotic nail, surgical suture and various types of stents can reach sufficient service life to complete the task and goal of tissue repair. And the Cu element can improve the strength of the zinc alloy and simultaneously has excellent antibacterial performance, so that the capability of the zinc alloy in practical medical application can be obviously improved. Therefore, the addition of Mn and Cu makes the zinc alloy wire prepared in this example have wider application in the medical field.

The zinc alloy ingot of the present embodiment contains up to 1 wt.% of Li, 0 to 1 wt.% of Mn, and/or 0 to 5 wt.% of Cu, with the balance being Zn, all in mass%.

Specifically, in some embodiments, the composition of the zinc alloy ingot may include 0-1 wt.% (excluding 0) Li, 0-1 wt.% Mn, and the balance Zn.

In other embodiments, the composition of the zinc alloy ingot may include 0-1 wt.% (excluding 0) Li, 0-5 wt.% Cu, and the balance Zn.

In other embodiments, the composition of the zinc alloy ingot may include 0-1 wt.% (excluding 0) of Li, 0-1 wt.% of Mn, and 0-5 wt.% of Cu, with the balance being Zn.

Further, the protective atmosphere in this example is CO₂And SF₆The mixed gas of (1).

Still to be noted, the cooling process of this embodiment is performed by a standing method, which can effectively promote the impurity to settle, thereby improving the purity of the alloy material.

And S120, carrying out homogenization treatment on the zinc alloy cast ingot, and then carrying out hot extrusion to obtain a zinc alloy bar.

Specifically, the zinc alloy ingot obtained in the step S110 is subjected to homogenization treatment under the conditions that the treatment temperature ranges from 220 ℃ to 270 ℃ and the heat preservation time ranges from 1h to 3 h. And then, carrying out hot extrusion treatment on the homogenized zinc alloy cast ingot under the conditions that the extrusion temperature range is 130-230 ℃, the extrusion ratio range is 14-18 and the extrusion speed range is 1-3 mm/s, so as to obtain a zinc alloy bar with the diameter range of 2-3 mm, and referring to fig. 2.

S130, performing multi-pass reciprocating drawing treatment and graded annealing treatment on the zinc alloy bar to obtain the medical zinc alloy wire.

Specifically, carry out multichannel reciprocating drawing to zinc alloy rod and handle, include: the drawing direction of each pass of drawing treatment on the zinc alloy bar is opposite to that of the previous pass; wherein, the deformation range of single pass is 5% -25%, and the deformation of each pass of drawing treatment is increased in a gradient manner. Referring to FIG. 3, 1 represents a zinc alloy wire during drawing, 2 represents a drawing die, and P is an axial force applied to the wire during the first drawing (or in the same direction as the drawing); n is the acting force of the inner wall of the die on the wire in the drawing process (the section view can only show two directions, and actually is circumferential stress); p' is the axial force experienced by the wire during the second pass (or in the same direction as this) of drawing.

The zinc alloy bar of the present example was subjected to the above-described multiple reciprocal drawing processes to obtain a filament having a diameter of 1mm or less.

The reciprocal drawing that this embodiment adopted is a novel mode of drawing for the silk material receives two opposite direction axial force actions just in time in drawing the in-process short time, the cooperation increases the single pass deflection gradually, the two can offset each other the axial effect of silk material, thereby the serious anisotropy and the composition segregation phenomenon that often appear in having weakened one-way drawing greatly, and then the internal structure appearance of zinc alloy silk material has been improved, make axial and radial mechanical properties obtain good homogeneity and balance, avoid simultaneously because of local inhomogeneous corrosion fracture inefficacy.

Further, the graded annealing treatment of the embodiment includes a first-stage annealing treatment in an air environment, wherein the temperature range of the first-stage annealing treatment is 150-300 ℃, and the heat preservation time range is 10-30 min. And performing second-stage annealing treatment in distilled water environment, wherein the temperature range of the second-stage annealing treatment is 60-80 ℃, and the heat preservation time range is 8-12 min. That is, in this embodiment, the medical zinc alloy wire is obtained by performing a plurality of reciprocating drawing processes on the zinc alloy bar to obtain a filament, and then performing a graded annealing process, as shown in fig. 4.

The whole annealing treatment process of the embodiment is divided into two-stage treatment, the zinc alloy wire is respectively in the two different environments in the graded annealing treatment, the graded annealing and the rapid cooling enable the organization structure and the distribution of the zinc alloy wire to be more uniform, and the stress effect and the component segregation hazards caused by extrusion and drawing in the wire are effectively removed. In addition, the treatment and heat preservation time required in the whole grading annealing process is shorter than that of the traditional heat treatment, so that the preparation efficiency and the preparation cost of the zinc alloy wire are greatly improved.

The diameter range of the medical zinc alloy wire obtained based on the preparation method of the embodiment is 0.1 mm-0.5 mm.

In another aspect of the invention, a medical zinc alloy wire is provided, which is prepared by the method described above.

In another aspect of the present invention, an application of the medical zinc alloy wire is provided, and the medical zinc alloy wire described above can be applied to at least one of an anastomosis nail, an absorbable surgical suture, a vascular stent, an intestinal stent, a tracheal stent and a urethral stent.

The following will further explain the preparation method of the medical zinc alloy wire material by combining the specific embodiment:

the preparation method of the medical zinc alloy wire in the example comprises the following steps:

s1, selecting zinc with the purity of 99.99 percent, lithium with the purity of 99.9 percent, zinc-manganese alloy and zinc-copper alloy as raw materials. Firstly, placing a crucible containing 6.5-6.8 kg of pure zinc into a resistance furnace, heating to 450 ℃ until the zinc is completely melted, raising the temperature of the furnace to 600 ℃ after the pure zinc is completely melted, and introducing CO₂And SF₆The mixed gas protection atmosphere of (1) adding pure lithium with good quality into the crucible, adding a proper amount of zinc-manganese alloy for melting after the pure lithium is completely melted, and finally adding zinc-copper alloy into the crucible. Stirring uniformly, standing for 30min, and stirring again to stand for 10min after the metal is completely melted. And after the furnace temperature is reduced to 500 ℃, taking the crucible out of the resistance furnace, and slowly pouring the liquid in the crucible into the cylindrical mold by using a funnel-shaped pouring tool. And after the pouring is finished, the die is cooled to room temperature in air, so that the alloy components in the die are fully solidified to obtain a zinc alloy ingot, and meanwhile, the impurity sedimentation is promoted, and the material purity is improved.

It should be noted that the specific mass of the raw materials in this example can be calculated according to the mass percentages in table 1.

TABLE 1 chemical composition content of medical zinc alloy wire

It is further noted that the zinc alloy ingot after casting and cooling is taken out of the mold, the scale and the necking of the cross section of the zinc alloy ingot are removed by a cutting machine, and then a cylindrical ingot with the same cross section area and the height of 4cm is cut. And finally, cutting a plurality of cylindrical materials with the cross section diameter of 1cm and the height of 4cm on the small ingot by using a wire cutting machine, and using the cylindrical materials as hot-pressing raw materials.

S2, placing the plurality of cylindrical zinc alloy cast ingots obtained in the step S1 in a heat preservation box at 250 ℃ for homogenization treatment, wherein the heat preservation time is 2 hours. After the heat preservation is finished, the mixture is immediately placed in an extruder die and coated with a proper amount of hot pressing oil. Then, the cast ingot is extruded at an extrusion ratio of 16 and an extrusion speed of 2mm/s, and finally, a medical zinc alloy bar with the diameter of 2.5mm is obtained, as shown in figure 2.

S3, rolling the zinc alloy bar obtained in the step S2, and then putting the zinc alloy bar into a die of a drawing machine, wherein the size of the die used in the embodiment is 2.6 mm. Specifically, the zinc alloy bar is firstly drawn from the head to the tail, then is replaced to a small-size die and is drawn from the tail to the head, and the deformation of a single pass is 5-25%. The stress of the bar during drawing is shown in figure 3. The above-mentioned steps are repeated to finally draw the zinc alloy bar into a fine wire having a diameter of 1mm or less.

Further, the prepared filaments are subjected to graded annealing, the first-stage annealing is an air environment at the temperature of 150-300 ℃, the temperature is kept for 10-30min, the second-stage annealing is a distilled water environment at the temperature of 60-80 ℃, the temperature is kept for 10min, the filaments are taken out and then cooled to room temperature in air, and finally the medical zinc alloy filaments after the graded annealing treatment are obtained, wherein the diameter of the medical zinc alloy filaments is 0.23mm, and is shown in figure 4.

The invention provides a medical zinc alloy wire and a preparation method and application thereof, and compared with the prior art, the medical zinc alloy wire has the following beneficial effects: first, the zinc alloy wire of the present invention comprises Mn and Cu elements, wherein the Mn element can improve the plasticity of the zinc alloy to a certain extent and keep the strength thereof stable. The Cu element can improve the strength of the zinc alloy and has excellent antibacterial performance. Secondly, the invention adopts a processing technology of multi-channel reciprocating drawing, so that the wire is subjected to two axial forces with opposite directions in a short time in the drawing process, and the two axial forces can counteract each other by matching with the gradually increased single-pass deformation, thereby greatly weakening the phenomena of serious anisotropy and component segregation which often occur in unidirectional drawing, further improving the internal structure appearance of the zinc alloy wire, ensuring that the axial and radial mechanical properties obtain excellent uniformity and balance, and avoiding the fracture failure caused by local uneven corrosion. Thirdly, the invention adopts a processing technology of graded annealing. The zinc alloy wire is respectively carried out in two different environments in the graded annealing treatment, the graded annealing and the rapid cooling make the organization structure and the distribution of the zinc alloy wire more uniform, and the stress action and the component segregation hazards caused by extrusion and drawing in the wire are effectively removed. In addition, the treatment and heat preservation time required in the whole grading annealing process is shorter than that of the traditional heat treatment, so that the preparation efficiency and the preparation cost of the zinc alloy wire are greatly improved.

It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.