CN112899527B - Degradable zinc alloy bar and preparation method thereof - Google Patents
Degradable zinc alloy bar and preparation method thereof Download PDFInfo
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- CN112899527B CN112899527B CN202110076919.9A CN202110076919A CN112899527B CN 112899527 B CN112899527 B CN 112899527B CN 202110076919 A CN202110076919 A CN 202110076919A CN 112899527 B CN112899527 B CN 112899527B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
Abstract
The invention provides a degradable zinc alloy bar and a preparation method thereof, wherein the zinc alloy bar is composed of Zn, Mg, Li and Mn, and the components by mass percent are 4-11% of Mg, 0.15-0.35% of Li, 0.7-1.0% of Mn, and the balance of Zn and inevitable impurities. The mechanical property of the zinc alloy bar material meets the requirements of strength and toughness of a medical implant material, is nontoxic, can be absorbed in a human body environment, and can avoid the pain of a patient caused by secondary operation; the corrosion resistance is much higher than that of magnesium alloy, the degradation speed is greatly reduced, mechanical support for a longer time can be provided, and early failure of the intravascular stent is avoided. In addition, the mechanical strength of the material is far higher than that of a polymer, the material is high in toughness, easy to manufacture, good in matching of elastic modulus and a human body, and capable of meeting two requirements of high corrosion resistance and high toughness.
Description
Technical Field
The invention relates to the field of medical implant materials, in particular to a degradable zinc alloy bar and a preparation method thereof.
Background
Degradable medical materials in the human body are becoming the focus of research and development, among which degradable high molecular materials, pure iron and iron-based alloys, pure magnesium and magnesium-based alloys are the most deeply studied materials in recent years. The degradable high polymer material has too low strength, and can be broken frequently in the clinical use process, and the clinical applicability is greatly limited. Pure iron and iron-based alloys have much higher strength and toughness than polymeric materials, but iron degrades too slowly and can degrade completely for years. More seriously, the rust-like substances produced during iron degradation expand several times in volume and have a pronounced tendency to migrate. The degradation products of pure magnesium and magnesium-based alloy are nontoxic and degradable, but the corrosion resistance is very poor, and the degradation products can be degraded quickly in human bodies and can not provide enough mechanical support time.
Corrosion behavior studies have shown that zinc may be more suitable as a degradable implant material than magnesium, iron. Zinc ions are essential nutrient elements of human bodies and participate in a large number of metabolic activities of the human bodies, and the American clinical innovation organization recommends that the human bodies must take 2.5-6.4 mg of zinc every day, and adults take about 300 mg of zinc every day to possibly have certain toxic reaction. It has also been found that zinc ions are transported very rapidly in human tissue, and therefore zinc-based degradable implantable devices do not exhibit zinc enrichment, cytotoxicity or necrosis in the vicinity. However, pure Zn has poor mechanical properties, compressive strength less than 20MPa, and elongation of only 0.2%, which is far from meeting clinical requirements, and implantable medical devices (such as bone plate nails, cardiac coronary stents, peripheral vascular stents, etc.) require materials with sufficient mechanical properties during service. Alloying is an effective method and a main means for improving the mechanical property of zinc, so that a zinc alloy bar with proper corrosion degradation rate and sufficient mechanical strength is needed to be provided.
Disclosure of Invention
The invention provides a degradable zinc alloy bar and a preparation method thereof, and aims to solve the problem that the existing implanted zinc alloy cannot give consideration to both degradation rate and mechanical strength.
In order to achieve the purpose, the invention provides a degradable zinc alloy bar which is composed of Zn, Mg, Li and Mn, and the mass percentage composition of the zinc alloy bar is 6-9% of Mg, 0.05-0.25% of Li, 0.5-0.9% of Mn, and the balance of Zn.
The application also provides a preparation method of the zinc alloy bar, which comprises the following steps:
firstly, batching according to the composition of zinc alloy, melting under protective gas to obtain a melt, and then stirring, standing and pouring to obtain a Zn-Mg series high-plasticity zinc alloy ingot;
secondly, sequentially extruding, drawing and annealing the obtained zinc alloy cast ingot to obtain a zinc alloy cylindrical bar with superplasticity characteristics;
thirdly, performing heat treatment on the obtained zinc alloy cast ingot for 300min, and then performing rotary swaging on the zinc alloy cast ingot to obtain a zinc alloy bar.
Further, the stirring speed is 500-1500r/min, and the stirring time is 10-20 min.
Further, in the step, a protective gas is nitrogen or argon.
Further, the nitrogen pressure is 2-10MPa in the pouring process, meanwhile, a high-energy ultrasonic probe is inserted into the alloy melt, the frequency of the high-energy ultrasonic equipment is 10-20KHz, and the high-energy ultrasonic treatment time is 10-20 min.
Further, the outer diameter of the zinc alloy ingot obtained in the first step is 40mm, and the height of the zinc alloy ingot is 80 mm.
Furthermore, the outer diameter of the swaged part in the third step is 20-25 mm.
The method of the invention utilizes the characteristic that Zn alloy is easy to corrode, and selects Zn-Mg series alloy as degradable material to be applied to human body implantation metal. The Zn-Mg series alloy of the invention has mechanical properties meeting the requirements of strength and toughness of human body implanted metal, can be degraded in vivo, not only can overcome the defects that medical polymer materials have low strength and traditional medical metal materials such as 316L stainless steel, titanium alloy and the like are not degraded, but also can overcome the defect that the mechanical properties of the implanted body are lost due to the excessively high degradation rate of magnesium and magnesium alloy, and has the dual characteristics of 'biological corrosion degradation characteristic' and 'proper corrosion rate' to ensure that long-term effective mechanical support is provided.
Mg2+ released by magnesium in human body can promote the growth, proliferation and differentiation of osteoblast, and has good bone induction effect. However, magnesium is a degradable metal in vivo, but has high activity, is rapidly degraded in vivo, and also generates hydrogen gas during degradation to form bubbles, which causes problems such as healing and inflammation. Zinc is also degradable, but at a slower rate. The prior art provides a zinc-magnesium alloy containing 15.5-48.5 wt.% of Mg15, which is used for coordinating the degradability of zinc and magnesium, and the zinc-magnesium alloy has proper degradation rate in body fluid, thereby overcoming the problems of fast magnesium degradation and generation of hydrogen bubbles, and also overcoming the problems of slow zinc degradation and influence on bone growth. However, the addition of such a large amount of magnesium significantly increases the production cost; and Mn, Li and the like are often used as alloy elements and are added into the zinc alloy in small amount, so that the degradation rate of the zinc alloy can be controlled, and the strength, the plasticity and the corrosion resistance of the zinc alloy can be improved.
Through the research of a Zn-based alloy phase diagram, the inventor finds that when the Mn content is lower than 0.5%, the strength of the alloy is not obviously improved, and when the Mn content exceeds 0.9%, a large number of irregularly-shaped MnZn13 second-phase particles and MnZn13 second-phase particles appear in a solidified structure of the alloy, so that a chain structure is weakened in a grain boundary, a rapid channel for crack propagation and stress corrosion is formed, the plasticity and corrosion resistance of the zinc alloy are remarkably reduced, and the degradation speed of the zinc alloy is accelerated; therefore, the invention provides that the Mn content in the zinc alloy is 0.5-0.9%, and the strength, the toughness and the corrosion resistance of the alloy can be obviously improved.
Experiments show that the effect of obviously strengthening the matrix can be achieved by adding Li into the Zn-Mg-Mn alloy, and the comprehensive effect of Mn and Li can be used for more obviously enhancing the strength and the plasticity of the zinc-magnesium alloy. According to research, the yield strength of the alloy is 250MPa and the tensile strength is more than 350MPa only when the content of Li in the Zn-Li binary alloy exceeds 0.5%, but the yield strength of the alloy is more than 250MPa and the tensile strength is more than 350MPa when the content of Li in the Zn-Mg-Mn-Li quaternary alloy is 0.05%, which benefits from the comprehensive effect of Mn and Li. The inventors have also found that, when the Li content exceeds 0.25%, although the strength of the Zn-Mg-Mn-Li alloy is further improved, there is a significant influence on the unevenness of the alloy structure and the corrosion resistance, which is disadvantageous in mass production of products having stable properties using the zinc alloy and increases the difficulty in surface treatment of products having requirements for surface smoothness. Therefore, the invention provides that the Li content in the zinc alloy is 0.05-0.25% by comprehensively considering the advantages and disadvantages of the Li element addition.
The mechanical property of the zinc alloy bar material meets the requirements of strength and toughness of a medical implant material, is nontoxic, can be absorbed in a human body environment, and can avoid the pain of a patient caused by secondary operation; the corrosion resistance is much higher than that of magnesium alloy, the degradation speed is greatly reduced, mechanical support for a longer time can be provided, and the early failure of the bar is avoided. In addition, the mechanical strength of the material is far higher than that of a polymer, the material is high in toughness, easy to manufacture, good in matching of elastic modulus and a human body, and capable of meeting two requirements of high corrosion resistance and high toughness.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
Aiming at the existing problems, the invention provides a degradable zinc alloy bar, which comprises, by mass, 6-9% of Mg, 0.05-0.25% of Li, 0.5-0.9% of Mn and the balance of Zn and inevitable impurities.
The preparation method of the zinc alloy bar comprises the following steps:
preparing materials according to the composition of the zinc alloy, melting under the protection of nitrogen, stirring, standing and casting, adding atmospheric nitrogen pressure in the forming process, and carrying out high-energy ultrasonic treatment to obtain a Zn-Mg series zinc alloy ingot; the stirring speed is 500-1500r/min, and the stirring time is 10-20 min; the high-energy ultrasonic frequency is 10-20KHz, and the processing time is 10-20 min; the nitrogen pressure is 2-10 MPa; the outer diameter of the cast ingot is 40mm, and the height of the cast ingot is 80 mm; sequentially extruding, drawing and annealing the obtained zinc alloy cast ingot to obtain a zinc alloy cylindrical bar with superplasticity characteristics; and performing rotary swaging on the obtained zinc alloy cast ingot after heat treatment for 300min to obtain a zinc alloy bar. The rotary swaging temperature is 300 ℃, and the outer diameter of the zinc alloy bar is 20-25 mm.
Example 1
The degradable zinc alloy bar is prepared by the preparation method, and the degradable zinc alloy bar comprises 6 mass percent of Mg, 0.05 mass percent of Li, 0.5 mass percent of Mn and the balance of Zn.
Example 2
The degradable zinc alloy bar is prepared by the preparation method, and the degradable zinc alloy bar comprises 9 mass percent of Mg, 0.10 mass percent of Li, 0.6 mass percent of Mn and the balance of Zn.
Example 3
The degradable zinc alloy bar is prepared by the preparation method, and the degradable zinc alloy bar comprises 8 mass percent of Mg, 0.15 mass percent of Li, 0.7 mass percent of Mn and the balance of Zn.
Table 1 shows the results of mechanical property data of examples
| Serial number | Experimental Material | Tensile strength/MPa | Elongation after fracture |
| 1 | Example 1 | 323 | 46 |
| 2 | Example 2 | 370 | 49 |
| 3 | Example 3 | 412 | 37 |
Table 2 shows the results of corrosion performance data of examples
| Serial number | Experimental Material | Degradation speed (mm/year) |
| 1 | Example 1 | 0.022 |
| 2 | Example 2 | 0.027 |
| 3 | Example 3 | 0.031 |
According to experimental data, the alloy bar with higher obdurability is obtained after zinc alloy crystal grains are refined through a plurality of strengthening processing technology improvements, particularly, the elongation of the zinc alloy material is greatly improved through the vibration treatment of the zinc alloy by high-energy ultrasound, the cost is reduced for product processing, and better raw materials are provided. The zinc alloy material prepared by the scheme has excellent obdurability, elongation and degradation performance, can be used for manufacturing orthopedic implants (such as bone screws and bone fracture plates) and cardiovascular stents, can provide good mechanical performance, does not need to be taken out for the second time, and reduces the pain of patients and the treatment cost.
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 (2)
1. A degradable zinc alloy bar is characterized in that,
the composition by mass percent is 6-9% of Mg, 0.05-0.25% of Li, 0.5-0.9% of Mn, and the balance of Zn and inevitable impurities;
the preparation method of the zinc alloy bar comprises the following steps:
preparing materials according to the composition of the zinc alloy, melting under the protection of nitrogen, stirring, standing and casting, adding atmospheric nitrogen pressure in the forming process, and carrying out high-energy ultrasonic treatment to obtain a Zn-Mg series zinc alloy ingot; the stirring speed is 500-1500r/min, and the stirring time is 10-20 min; the high-energy ultrasonic frequency is 10-20KHz, and the processing time is 10-20 min; the nitrogen pressure is 2-10 MPa; the outer diameter of the cast ingot is 40mm, and the height of the cast ingot is 80 mm; sequentially extruding, drawing and annealing the obtained zinc alloy cast ingot to obtain a zinc alloy cylindrical bar with superplasticity characteristics; performing rotary swaging on the obtained zinc alloy cast ingot after heat treatment for 300min to obtain a zinc alloy bar; the rotary swaging temperature is 300 ℃, and the outer diameter of the zinc alloy bar is 20-25 mm.
2. A method of making a zinc alloy bar according to claim 1, comprising the steps of:
the composition by mass percent is 6-9% of Mg, 0.05-0.25% of Li, 0.5-0.9% of Mn, and the balance of Zn and inevitable impurities;
the preparation method of the zinc alloy bar comprises the following steps:
preparing materials according to the composition of the zinc alloy, melting under the protection of nitrogen, stirring, standing and casting, adding atmospheric nitrogen pressure in the forming process, and carrying out high-energy ultrasonic treatment to obtain a Zn-Mg series zinc alloy ingot; the stirring speed is 500-1500r/min, and the stirring time is 10-20 min; the high-energy ultrasonic frequency is 10-20KHz, and the processing time is 10-20 min; the nitrogen pressure is 2-10 MPa; the outer diameter of the cast ingot is 40mm, and the height of the cast ingot is 80 mm; sequentially extruding, drawing and annealing the obtained zinc alloy cast ingot to obtain a zinc alloy cylindrical bar with superplasticity characteristics; performing rotary swaging on the obtained zinc alloy cast ingot after heat treatment for 300min to obtain a zinc alloy bar; the rotary swaging temperature is 300 ℃, and the outer diameter of the zinc alloy bar is 20-25 mm.
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