CN109128064B - Biodegradable Zn-Na series zinc alloy and preparation method thereof - Google Patents

Biodegradable Zn-Na series zinc alloy and preparation method thereof Download PDF

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CN109128064B
CN109128064B CN201811108848.0A CN201811108848A CN109128064B CN 109128064 B CN109128064 B CN 109128064B CN 201811108848 A CN201811108848 A CN 201811108848A CN 109128064 B CN109128064 B CN 109128064B
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zinc alloy
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zinc
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CN109128064A (en
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石章智
刘雪峰
王鲁宁
于静
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Beijing Shangning Kezhi Medical Instrument Co ltd
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University of Science and Technology Beijing USTB
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Abstract

A biodegradable Zn-Na series zinc alloy belongs to the field of medical implant materials. In the alloy: na is 0.01 to 0.97%. And at least one of 27 elements harmless or beneficial to human body is selected. In order to reduce the cost and obtain excellent comprehensive performance, the total amount of various added alloy elements is optimally controlled to be not more than 2.0 percent, and the balance is Zn. The preparation and processing flow of the zinc alloy is as follows: continuous casting → hot extrusion → rolling, continuous casting → hot extrusion → solution heat treatment → drawing, or continuous casting → homogenization heat treatment → hot extrusion → rolling. The yield strength of the zinc alloy is 100-500 MPa, the tensile strength is 150-700 MPa, and the elongation is 1.5-100%; the degradation rate in simulated body fluid does not exceed 0.8 mm/year; the cytotoxicity to L929 cells and human bone marrow mesenchymal stem cells is grade 0 or grade 1, shows good biocompatibility, and can be used for various medical implants.

Description

Biodegradable Zn-Na series zinc alloy and preparation method thereof
Technical Field
The invention relates to the field of component design, preparation methods and application of biodegradable Zn-Na series zinc alloy, and belongs to the field of medical implant materials.
Background
Zinc ranks the top five in metal production and consumption worldwide and is mainly used for zinc-containing articles such as coatings, cast alloys, batteries, brass, etc., the most important use of which is the corrosion protection of steel. Zinc is a trace element necessary for human body and can be used as biodegradable metal. However, the tensile strength of zinc is only 120MPa, which cannot meet the requirements of various medical implants on the mechanical properties of materials, and greatly limits the application range of zinc as biodegradable metal. Zinc and zinc alloys are extremely brittle as cast and typically have room temperature elongation of less than 3%, severely limiting their use.
Sodium (Na) is an essential nutrient element in the human body, is distributed in the blood and extracellular fluid, plays an important role in maintaining the fluid balance, and also assists the normal operation of muscles, heart and nerves. The Na content of human body is 105 g, and the Na content of blood is 3.15-3.40 g/L under normal condition. The human body loses about 115 mg of Na daily through epidermal sweating, urine and excreta. Adults are recommended to ingest 2.3 grams of Na daily, 1.5-2.2 grams for children and juveniles, mainly through the diet, especially salt.
Patent document 1 discloses a high wear-resistant high thermal conductivity zinc alloy containing strontium and sodium and a processing process thereof, wherein the high wear-resistant high thermal conductivity zinc alloy comprises the following components in percentage by mass: na: 0.8 to 1.2%, Sr: 0.2-0.3%, In: 4.5-6.3%, Zr: 0.8-1.2%, Si: 0.4-0.8%, Sn: 2.4-3.6%, Yb: 0.2-0.5%, Nd: 0.1-0.2%, S: 0.8-1.0% and the balance of zinc. The tensile strength of the zinc alloy is 580 to 720MPa, but patent document 1 does not provide the yield strength and elongation of the zinc alloy. The zinc alloy contains Yb, and the compound of this element causes irritation to eyes and skin of a human and may cause teratogenesis. Therefore, the alloy cannot be used as a medical implant material.
Patent document 2 discloses a Na — Er — Mo zinc aluminum alloy for cold stamping hot dip coating, which contains, in mass%: na: 0.5-0.6%, Mg: 3.0-4.0%, Ca: 1.5-1.8%, Al: 25.0-28.0%, Se: 0.1-0.2%, Er: 0.2-0.4%, B: 0.1-0.2%, Mo: 0.3-0.5% and the balance of zinc. The element added in the zinc alloy in the highest amount is Al, which may cause nervous system diseases. Therefore, the zinc alloy is not suitable as a medical implant material.
Patent document 3 discloses a Na-containing rapidly degradable magnesium alloy and a preparation method thereof, which comprises the following components in mass%: al: 3.0-12%, Zn: 0.5-5%, Cu: 0.5-3%, Na: 0.1 to 1.0% and the balance of Mg and inevitable impurities. The magnesium alloy is used for soluble bridge plugs used in fracturing construction of oil and gas fields.
Patent document 4 discloses an aluminum alloy and a method for producing the same, the composition of which is, in mass%: mg: 0.55-0.65%, Mn: 0.25-0.3%, Cr: 0.1-0.2%, Si: 0.7-0.75%, Fe: 0.1 to 0.25%, Cu: 0.4-0.45%, Ti: 0.02-0.06%, Na: 0.15-0.20%, and the balance of Al. The aluminum alloy has high corrosion resistance and excellent formability and weldability.
Documents of the prior art
Patent document 1: CN108004432A, strontium-and sodium-containing high-wear-resistance high-heat-conductivity zinc alloy and processing technology thereof
Patent document 2: CN108396196A Na-Er-Mo zinc-aluminum alloy for cold stamping hot dip coating without zinc flowers
Patent document 3: CN107523732A, Na-containing rapidly-degradable magnesium alloy and preparation method thereof
Patent document 4: CN104178668B, aluminum alloy and preparation method thereof
Disclosure of Invention
Problems to which the present invention is directed
The pure zinc has low strength and is difficult to adapt to the requirements of various medical implant devices on the mechanical properties of materials. The alloying is combined with the optimization design of the preparation processing technology to be an effective means for improving the mechanical property of pure zinc, and the existing high-performance biodegradable zinc alloy has few varieties and can not adapt to the market demand. The development of novel and high-performance biodegradable zinc alloy is a problem to be solved urgently at the present stage.
A biodegradable Zn-Na series zinc alloy is characterized in that the alloy comprises the following chemical components in percentage by mass: na accounts for 0.01-0.97%, and NaZn is contained in the zinc alloy13The volume fraction of (A) is 0.4-40%.
Further, the alloy is selected to add at least one of the following 27 elements: c: 0.003 to 3.4%, Sn: 0.01-10.2%, B: 0.003-3.1%, Ge: 0.007-7.6%, Se: 0.004-4.1%, P: 0.002-1.6%, Ag: 0.004 to 4.0%, Li: 0.002-0.82%, Cu: 0.018-6.0%, Mg: 0.005-2.0%, Ce, Pr, Nd, Sm, Ho: 0.017-4.2%, Er, Gd, Lu: 0.019-4.7%, K: 0.004-1.0%, La: 0.014 to 3.5%, Ca, Ti: 0.005-1.1%, Fe, Mn, Mo: 0.006-1.5%, Sr, Zr: 0.009-2.3%.
A preparation method of biodegradable Zn-Na series zinc alloy comprises the following processing flows:
(1) continuous casting → hot extrusion → rolling;
(2) continuous casting → hot extrusion → solution heat treatment → drawing;
(3) continuous casting → homogenizing heat treatment → hot extrusion → rolling.
Further, the smelting temperature of the continuously cast alloy raw material in the step (1) is 580-880 ℃, the continuous casting is started after vacuumizing or inert gas protection is conducted, the temperature is kept for 5-20 minutes, the casting mold is heated to 430-550 ℃ higher than the melting point of the zinc alloy, circulating water with the temperature kept at 5-27 ℃ is used for cooling the continuous casting billet outside the outlet of the casting mold, and the billet drawing speed is 0.3-10 cm/min.
Further, the hot extrusion in the step (2) or (3) is carried out at the temperature of 150-300 ℃, the extrusion speed is 1-8 mm/min, the extrusion ratio is 9-81, and the size of the second phase is thinned to be less than 50 μm.
Further, the rolling in the step (3) or (4) is carried out at room temperature to 320 ℃, the rolling speed is 0.01 to 0.1m/s, the deformation is 10 to 98 percent, and the grain size of zinc is refined to be less than 10 mu m.
Further, the drawing in the step (4) is carried out at room temperature to 280 ℃, and the deformation is 20 to 99.9 percent.
Further, the solution heat treatment in the step (3) is carried out in a vacuum or inert gas protection environment, the temperature is kept at 340-390 ℃ for 1-25 hours, then water quenching is carried out immediately, and 10-100% of coarse AgZn3、LiZn4、CuZn5、Mg2Zn11And MnZn13The second phase is solid-dissolved in the zinc matrix, so that the degradation safety of the zinc alloy in organisms is improved.
Further, the homogenization heat treatment in the step (2) is carried out in 2 steps under the vacuum or inert gas protection environment, the temperature is raised to 200-300 ℃ at the speed of 2-10 ℃/min and is kept for 1-4 hours, then the temperature is raised to 350-380 ℃ at the speed of 1-5 ℃/min and is kept for 1-3 hours, and then cooling is carried out, wherein the cooling mode comprises furnace cooling and water quenching.
The gist of the present invention is as follows.
Unless otherwise specified,% is by mass.
1. The invention provides the biodegradable Zn-Na series zinc alloy, which is characterized in that the biodegradable Zn-Na series zinc alloy comprises the following chemical components in percentage by mass: na: 0.01 to 0.97 percent. The Na content was determined as follows.
According to a Zn-Na binary phase diagram, at the Zn-rich end of the phase diagram, Na is combined with Zn to generate NaZn with the melting point of 548 DEG C13An intermetallic compound having a Na content of 2.6%. If the Na content exceeds 2.6%, the low melting point of NaZn is entered13In the + Na two-phase region, Na melting occurs when the temperature rises to 97.5 ℃, and Na enters into NaZn13The + L (Na-rich liquid phase) two-phase region causes the zinc alloy to undergo corrosion, significantly reducing the alloy properties. The invention therefore proposes that the Na content in the zinc alloy is less than 2.6%.
Further, the invention proposes to control NaZn13The volume fraction of the zinc alloy is 0.4-40%, and the Na content of the zinc alloy is further optimized. Because of the NaZn13The deformability of the intermetallic compound is significantly lower than that of Zn, when NaZn13Above 40%, the brittleness of the zinc alloy increases significantly, resulting in a high susceptibility to cracking and, in severe cases, failure at break during plastic working. The density of Zn is 7.14g/cm3The Applicant has come to the study of NaZn13Its density was calculated to be 6.26g/cm3And calculating by using a lever law to obtain the Na content and the NaZn content in the zinc alloy13As a function of the volume fraction of (c). According to the calculation result of the applicant, the NaZn is obtained when the Na content is 0.01-0.97 percent13The volume fraction of (A) is 0.4-40%.
2. The invention provides a biodegradable Zn-Na series zinc alloy which is characterized in that chemical components are calculated by mass percent, and at least one of the following 27 elements which are nontoxic or beneficial to human bodies can be further added: lithium (Li), potassium (K), carbon (C), germanium (Ge), cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), holmium (Ho), erbium (Er), gadolinium (Gd), lutetium (Lu), molybdenum (Mo), tin (Sn), phosphorus (P), boron (B), selenium (Se), zirconium (Zr), calcium (Ca), magnesium (Mg), iron (Fe), manganese (Mn), copper (Cu), silver (Ag), strontium (Sr) and titanium (Ti). The basis for determining the addition amounts of the above elements is as follows.
According to the thermodynamic theory and the database of materials, the invention proposes to group the additive elements according to the binding capacity of the additive elements and Zn atoms so as to determine the volume fraction range of the additive elements and the Zn atoms in the zinc alloy, and the volume fraction range is used as a basis for controlling the content of the additive elements so as to optimize the mechanical property, particularly the plasticity of the zinc alloy. The elements are grouped as follows:
(1) group 1 includes 7 elements: C. sn, B, Ge, Se, P and Ag. Atoms of a single element can be combined with 0-3 Zn atoms to form a second phase, wherein C, Sn, B and Ge exist in a Zn matrix in a simple substance form, and Se, P and Ag are combined with Zn to form ZnSe and Zn3P2And AgZn3。
(2) Group 2 includes 3 elements: li, Cu and Mg. The atoms of a single element can combine with 4-6 Zn atoms to form a second phase: LiZn4、CuZn5And Mg2Zn11。
(3) Group 3 includes 17 elements: ce. Pr, Nd, Sm, Ho, Er, Gd, Lu, K, La, Ca, Fe, Mn, Sr, Zr, Ti and Mo. The atoms of a single element can be combined with 11-22 Zn atoms to form a second phase: CeZn11、PrZn11、NdZn11、SmZn11～12、HoZn12、ErZn12、GdZn12、LuZn12、KZn13、LaZn13、CaZn13、FeZn13、MnZn13、SrZn13、ZrZn14、TiZn15And MoZn22。
The invention provides that the mechanical property of the zinc alloy is improved by utilizing the second phase, and the strength of the zinc alloy is improved by forming the second phase with nanometer size and micron size in the zinc crystal grains to block the application of dislocation; the recrystallization of zinc grains is promoted by forming a micron-sized second phase on the zinc grain boundary, the grains are refined, and the strength and the plasticity of the zinc alloy are improved.
The invention provides that the volume fraction of a second phase formed by elements in a control group 1 is 0.01-10%; the volume fraction of a second phase formed by the elements in the control group 2 is 0.1-35%; the volume fraction of the second phase formed by the elements in the control group 3 is 0.1-25%. The upper limit of the volume fraction of the second phase formed by the elements in groups 1 to 3 does not exceed the upper limit of the volume fraction of the second phase formed by the Na element. From this calculation, the content ranges of one of the 27 elements when added alone were found: c: 0.003 to 3.4%, Sn: 0.01-10.2%, B: 0.003-3.1%, Ge: 0.007-7.6%, Se: 0.004-4.1%, P: 0.002-1.6%, Ag: 0.004 to 4.0%, Li: 0.002-0.82%, Cu: 0.018-6.0%, Mg: 0.005-2.0%, Ce, Pr, Nd, Sm, Ho: 0.017-4.2%, Er, Gd, Lu: 0.019-4.7%, K: 0.004-1.0%, La: 0.014 to 3.5%, Ca, Ti: 0.005-1.1%, Fe, Mn, Mo: 0.006-1.5%, Sr, Zr: 0.009-2.3%.
3. The invention provides that the influence of the interaction among elements on the comprehensive performance of the zinc alloy is comprehensively considered, the alloy cost and the processing performance are considered, the total amount of various added alloy elements is controlled to be not more than 2.0 percent (in the actual production process, if the alloy cost is not considered, the comprehensive performance of the alloy is simply considered, the total amount of the various added alloy elements can be more than 2 percent), and the balance is Zn. The biodegradable Zn-Na series zinc alloy with low cost and low alloying is obtained. The mechanical property of the zinc alloy is obviously higher than that of pure zinc.
4. The invention provides a preparation processing flow and technological parameters of the zinc alloy, which are as follows:
(1) continuous casting → hot extrusion → rolling;
(2) continuous casting → hot extrusion → solution heat treatment → drawing;
(3) continuous casting → homogenizing heat treatment → hot extrusion → rolling.
The continuous casting alloy is smelted in a graphite or ceramic crucible, the smelting temperature is 580-880 ℃, the continuous casting is started after vacuumizing or inert gas protection is conducted, the temperature is kept for 5-20 minutes after the continuous casting is carried out, a graphite casting mold with a polished inner wall is used, the casting mold is heated to a temperature of 430-550 ℃ higher than the melting point of the zinc alloy, steel or copper is used as a dummy bar, circulating water with the temperature maintained at 5-27 ℃ is used for cooling a continuous casting blank outside the outlet of the casting mold, and the blank drawing speed is 0.3-10 cm/min. The temperature field of the continuous casting billet is controlled by adjusting the heating temperature of the casting mould, the blank drawing speed and the cooling strength, the solid-liquid interface of the zinc alloy continuous casting billet is controlled at a position of 0.2-3 cm in the outlet of the casting mould, and the continuous casting achieves the following effects: (1) the leakage accident in the continuous casting process is prevented, and the potential safety hazard is avoided; (2) the friction between the continuous casting billet and the casting wall is reduced, the withdrawal force is reduced, the continuous casting billet with excellent surface quality is obtained, the surface of the continuous casting billet is bright, thick oxide skin does not exist, and the continuous casting billet can be directly used for subsequent hot extrusion processing. The zinc alloy cast ingot prepared by the traditional method needs to remove oxide skin on the surface of the cast ingot before hot extrusion, so that the processing procedures are increased, the production cost is improved, and the production efficiency is reduced; (3) the oriented multiphase structure is obtained, wherein zinc crystal grains are columnar (columnar crystal), a second phase is distributed on a crystal boundary, and the included angle between the long axis direction of the columnar crystal and the length direction of the continuous casting billet is 0-15 degrees.
The hot extrusion is carried out at the temperature of 150-300 ℃, the extrusion speed is 1-8 mm/min, the extrusion ratio is 9-81, and the second phase is refined to the size of less than 50 mu m.
The rolling is carried out at room temperature to 320 ℃, the rolling speed is 0.01 to 0.1m/s, the deformation is 10 to 98 percent, and the zinc grains are refined to be less than 10 mu m in size.
The drawing is carried out at room temperature to 280 ℃, and the deformation is 20 to 99.9 percent.
The solid solution heat treatment is carried out in a vacuum or inert gas protection environment, the temperature is kept at 340-390 ℃ for 1-25 hours, and then the steel is immediately quenched in water (water quenching), wherein the water temperature is 0-40 ℃. The solution heat treatment is carried out on 10-100% of coarse AgZn3、LiZn4、CuZn5、Mg2Zn11And MnZn13The second phase is dissolved in the zinc matrix in a solid solution mode, so that the purpose of adjusting the microstructure of the zinc alloy is achieved, and the degradation safety of the zinc alloy in a human body is improved.
The homogenization heat treatment is carried out in 2 steps under the vacuum or inert gas protection environment, the temperature is raised to 200-300 ℃ at the speed of 2-10 ℃/min, the heat is preserved for 1-4 hours, then the temperature is raised to 350-380 ℃ at the speed of 1-5 ℃/min, the heat is preserved for 1-3 hours, and then the cooling is carried out. The cooling mode comprises furnace cooling and water quenching, and the water temperature is 0-40 ℃. The step 1 of the heat treatment is to prevent low-melting-point substances in the zinc alloy from melting, so that grain boundary ablation is caused, and the material is scrapped. The 2 nd step of the heat treatment is to homogenize the micro segregation and to improve the plastic formability and effect of the zinc alloy.
5. The biodegradable Zn-Na series zinc alloy has the room temperature tensile mechanical properties as follows: the yield strength is 100-500 MPa, the tensile strength is 150-700 MPa, and the elongation is 1.5-100%. The mechanical properties can be adjusted in the large range by adjusting the components and the preparation process of the zinc alloy, and the requirements of various medical implant devices on the mechanical properties of materials are met.
6. The degradation rate of the biodegradable Zn-Na series zinc alloy in simulated body fluid is not more than 0.8 mm/year.
7. The biodegradable Zn-Na series zinc alloy has cytotoxicity of 0 grade or 1 grade on L929 cells and human bone marrow mesenchymal stem cells, and shows good biocompatibility.
8. The biodegradable Zn-Na series zinc alloy of the invention is suitable for but not limited to manufacturing the following medical implant: coronary artery and other vascular stents, urethral stents, biliary stents, intracranial stents, tracheal stents, esophageal stents, intestinal stents, bone tissue repair stents, bone nails, bone needles, suture anchors, screws, bone plates, bone sleeves, intramedullary needles, intestinal staplers, vascular staplers or nerve staplers.
The characteristics and advantages of the invention are as follows:
1. the Zn-Na series zinc alloy has good biocompatibility, and the mechanical property, the biodegradation speed and the antibacterial property can be adjusted in a large range by adjusting alloy components and preparing and processing flows and parameters, so that the requirements of various medical implant devices on the material performance can be met, and the applicability is wide.
2. When the total amount of various alloy elements added in the Zn-Na series zinc alloy is not more than 2.0 percent, the mechanical property and the fatigue resistance are obviously superior to those of pure zinc.
3. The Zn-Na series zinc alloy has low cost, and the preparation process flow and parameters are easy to realize by using the existing industrial equipment, thereby being very suitable for industrial popularization.
Detailed Description
The following describes embodiments of the present invention in detail.
The invention relates to a biodegradable Zn-Na series zinc alloy and a preparation method thereof.
The effects of the present invention will be described more clearly by examples. The present invention is not limited to the following examples, and can be implemented by appropriately changing the examples without changing the gist thereof.
Example 1:
the components, preparation and performance test of the biodegradable Zn-Na binary zinc alloy.
The chemical compositions of 4 invention examples of the zinc alloy are shown in Table 1-1, and the added Na is 0.01-0.72%, and the balance is Zn. NaZn in the zinc alloy13The volume fraction of the second phase is 0.4 to 30%.
The preparation and processing flow of the zinc alloy is as follows: continuous casting → hot extrusion → rolling. The raw materials for continuous casting are metal Zn and metal Na which are proportioned according to the table 1-1, the metal Zn and the metal Na are placed into a graphite crucible of continuous casting equipment, high-purity argon is introduced for protection after vacuumizing, then the graphite crucible is heated to 620 ℃ through induction heating, the temperature is kept for 10 minutes until the raw materials are melted, and the raw materials are fully mixed under the stirring of electromagnetic force. Heating the graphite casting mold to 450 ℃, starting a blank drawing device to slowly draw the continuous casting slab out of the graphite casting mold, and keeping the circulating water temperature at 20 +/-1 ℃ to obtain the continuous casting slab with a bright surface, wherein zinc crystal grains are columnar crystals, and the included angle between the long axis direction of the zinc crystal grains and the length direction of the continuous casting slab is 0-10 degrees.
The hot extrusion is carried out at 220 ℃, the extrusion speed is 2mm/min, and the extrusion ratio is 16.
The rolling is carried out at 60 ℃, the rolling speed is 0.04m/s, the deformation is 60-98%, and the zinc alloy rolled material is prepared, wherein the average grain size of zinc grains is less than 10 mu m, and NaZn13The size of the second phase is less than 1 μm.
And cutting a sample from the zinc alloy rolled stock to test electrochemical corrosion, soaking corrosion, cytotoxicity and room temperature tensile mechanical properties. The test specimens for the above-mentioned performance tests were prepared in accordance with the methods in the relevant standards, the electrochemical corrosion rate was calculated in accordance with the ASTM-G102-89 standard, the immersion corrosion rate was calculated in accordance with the ASTM-G102-89 standard, the cytotoxicity was evaluated in accordance with the national standard GB/T16886.5-2003, and the tensile mechanical properties at room temperature were evaluated in accordance with the national standard GB/T228.1-2010.
The tensile mechanical properties at room temperature of 4 invention examples of zinc alloy in the table 1-1 are measured as follows: the yield strength is 100-180 MPa, the tensile strength is 150-220 MPa, and the elongation is 40-100%.
The electrochemical corrosion rate of the zinc alloy of 4 invention examples in the table 1-1 in simulated body fluid is measured to be 0.05-0.10 mm/year.
The soaking corrosion rate of the zinc alloy of 4 invention examples in the table 1-1 in simulated body fluid is measured to be 0.04-0.08 mm/year.
The cytotoxicity of 4 invention zinc alloys in the table 1-1 is measured to be 0 grade or 1 grade, and the zinc alloys show good biocompatibility.
TABLE 1-1
Examples of the invention Na (% by mass) NaZn13(vol%)
Alloy 1 0.01 0.4
Alloy 2 0.23 10
Alloy 3 0.35 15
Alloy 4 0.72 30
Example 2:
the components, preparation and performance test of the biodegradable Zn-Na series ternary zinc alloy.
The chemical components of 8 invention examples of the zinc alloy are shown in the table 2-1, the total amount of the added alloy elements is 0.25-0.98%, the balance is Zn, the zinc alloy belongs to low-alloying zinc alloy, and the cost is low.
The preparation and processing flow of the zinc alloy is as follows: continuous casting → hot extrusion → rolling. High-purity raw materials are used for mixing according to the content of elements in the table 2-1, the raw materials are placed in a graphite crucible of continuous casting equipment, high-purity argon is introduced for protection after vacuumizing, then the graphite crucible is heated to 650 ℃ through induction heating, the temperature is kept for 8 minutes until the raw materials are melted, and the raw materials are fully mixed under the stirring of electromagnetic force. Heating the graphite casting mold to 430 ℃, starting a blank drawing device to slowly draw the continuous casting slab out of the graphite casting mold, and keeping the circulating water temperature at 25 +/-1 ℃ to obtain the continuous casting slab with a bright surface, wherein zinc crystal grains are columnar crystals, and the included angle between the long axis direction of the zinc crystal grains and the length direction of the continuous casting slab is 0-10 degrees.
The hot extrusion is carried out at 200 ℃, the extrusion speed is 1mm/min, and the extrusion ratio is 25.
And rolling at room temperature at the rolling speed of 0.07m/s and the deformation of 60-80% to obtain the zinc alloy rolled material, wherein the average grain size of zinc grains is 1-5 mu m, and the sizes of various second phases are less than 2 mu m.
And cutting a sample from the zinc alloy rolled stock to test electrochemical corrosion, cytotoxicity and room-temperature tensile mechanical properties. The preparation and testing of the above samples was carried out as provided in example 1.
The tensile mechanical properties at room temperature of 8 invention examples of zinc alloy in the table 2-1 are measured as follows: the yield strength is 120-450 MPa, the tensile strength is 180-590 MPa, and the elongation is 5-60%.
The electrochemical corrosion rate of the zinc alloy of 8 invention examples in the table 2-1 in simulated body fluid is measured to be 0.05-0.23 mm/year.
The cytotoxicity of 8 invention examples of zinc alloy in the table 2-1 is measured to be 0 grade or 1 grade, and the zinc alloy shows good cell compatibility.
TABLE 2-1
Figure BDA0001808567190000091
Example 3:
the components, preparation and performance test of the biodegradable Zn-Na quaternary zinc alloy.
The zinc alloy contains 4 alloy elements, 2 of which are necessary alloy elements: zn and Na, and 3-4 kinds of alloying elements are further added. The chemical components of 18 embodiments of the zinc alloy are shown in the table 3-1, the total amount of the added alloy elements is 0.46-1.40%, the balance is Zn, the zinc alloy belongs to low-alloying zinc alloy, and the cost is low.
The preparation and processing flow of the zinc alloy is as follows: continuous casting → homogenizing heat treatment → hot extrusion → rolling. High-purity raw materials are used for mixing according to the content of elements in the table 3-1, the raw materials are placed in a graphite crucible of continuous casting equipment, high-purity argon is introduced for protection after vacuumizing, then the graphite crucible is heated to 700 ℃ through induction heating, and the temperature is kept for 5 minutes until the raw materials are melted and fully mixed under the stirring of electromagnetic force. Heating the graphite casting mold to 440 ℃, starting a blank drawing device to slowly draw the continuous casting slab out of the graphite casting mold, and keeping the circulating water temperature at 18 +/-1 ℃ to obtain the continuous casting slab with a bright surface, wherein zinc crystal grains are columnar crystals, and the included angle between the long axis direction of the zinc crystal grains and the length direction of the continuous casting slab is 0-10 degrees.
The homogenization heat treatment is carried out in a vacuum heat treatment furnace, after vacuumizing, the temperature is raised to 200 ℃ at the speed of 2 ℃/min and is preserved for 4 hours, then the temperature is raised to 360 ℃ at the speed of 1 ℃/min and is preserved for 2 hours, and then the furnace is cooled.
The hot extrusion is carried out at 250 ℃, the extrusion speed is 4mm/min, and the extrusion ratio is 16.
And rolling at room temperature at the rolling speed of 0.03m/s and the deformation of 82-93% to obtain the zinc alloy rolled material, wherein the average grain size of zinc grains is 1-5 mu m, and the sizes of various second phases are less than 1 mu m.
And cutting a sample from the zinc alloy rolled stock to test electrochemical corrosion, cytotoxicity and room-temperature tensile mechanical properties. The preparation and testing of the above samples was carried out as provided in example 1.
Samples were cut from the zinc alloy rolled stock and tested for antimicrobial properties. Firstly, cutting a sample into a wafer with the diameter of 10 multiplied by 2mm, polishing the wafer to obtain a surface with metal luster, putting the wafer into alcohol for ultrasonic cleaning for 20-40 minutes, and drying for later use after cleaning. The antibacterial property of the alloy is tested by adopting a flat plate coating method, and the antibacterial rate is calculated according to the following formula: the antibacterial ratio (%) - (average number of colonies in negative control group-average number of colonies in sample group)/average number of colonies in negative control group × 100%. The bacterium used for the test was E.coli.
The tensile mechanical properties at room temperature of 18 invention examples of zinc alloys in the table 3-1 are measured as follows: the yield strength is 200-420 MPa, the tensile strength is 260-550 MPa, and the elongation is 3-55%.
The electrochemical corrosion rate of the zinc alloy of 18 invention examples in the table 3-1 in simulated body fluid is measured to be 0.08-0.30 mm/year.
The cytotoxicity of 18 invention zinc alloys in the table 3-1 is measured to be 0 grade or 1 grade, and the zinc alloys show good cell compatibility.
The antibacterial rate of the alloy 14, 19, 20, 23, 24, 26-28 of the invention example in the table 3-1 is more than 90%, and the alloy has antibacterial property.
TABLE 3-1
Figure BDA0001808567190000101
Figure BDA0001808567190000111
Example 4:
the components, preparation and performance test of the biodegradable Zn-Na series quinary zinc alloy.
The zinc alloy contains 5 alloy elements, 2 of which are necessary alloy elements: zn and Na, and 3-5 kinds of alloying elements are further added. The chemical components of the 15 embodiments of the zinc alloy are shown in the table 4-1, the total amount of the added alloy elements is 0.44-1.37%, the balance is Zn, the zinc alloy belongs to low-alloying zinc alloy, and the cost is low.
The preparation and processing flow of the zinc alloy is as follows: continuous casting → homogenizing heat treatment → hot extrusion → rolling. High-purity raw materials are used for mixing according to the content of elements in the table 4-1, the raw materials are placed in a graphite crucible of continuous casting equipment, high-purity argon is introduced for protection after vacuumizing, then the graphite crucible is heated to 750 ℃ through induction heating, and the temperature is kept for 5 minutes until the raw materials are melted and fully mixed under the stirring of electromagnetic force. Heating the graphite casting mold to 500 ℃, starting a blank drawing device to slowly draw the continuous casting slab out of the graphite casting mold, and keeping the circulating water temperature at 15 +/-1 ℃ to obtain the continuous casting slab with a bright surface, wherein zinc crystal grains are columnar crystals, and the included angle between the long axis direction of the zinc crystal grains and the length direction of the continuous casting slab is 0-8 degrees.
The homogenization heat treatment is carried out in a vacuum heat treatment furnace, after vacuum pumping, the temperature is firstly raised to 250 ℃ at the speed of 4 ℃/min and is preserved for 3 hours, then the temperature is raised to 375 ℃ at the speed of 2 ℃/min and is preserved for 1.5 hours, and then the mixture is immediately put into water with the temperature of 0 ℃ for water quenching.
The hot extrusion is carried out at 225 ℃, the extrusion speed is 2mm/min, and the extrusion ratio is 16.
And rolling at room temperature at the rolling speed of 0.05m/s and the deformation of 83-98% to prepare the zinc alloy rolled material, wherein the average grain size of zinc grains is 1-5 mu m, and the sizes of various second phases are less than 1 mu m.
And cutting a sample from the extrusion rolled material of the zinc alloy to test electrochemical corrosion, cytotoxicity and room temperature tensile mechanical property. The preparation and testing of the above samples was carried out as provided in example 1.
The tensile mechanical properties at room temperature of 15 invention examples of zinc alloy in the table 4-1 are measured as follows: the yield strength is 260-500 MPa, the tensile strength is 320-700 MPa, and the elongation is 2-46%.
The electrochemical corrosion rate of the zinc alloy of 15 invention examples in the table 4-1 in simulated body fluid is measured to be 0.24-0.43 mm/year.
The cytotoxicity of 15 invention zinc alloys in the table 4-1 is measured to be 0 grade or 1 grade, and the zinc alloys show good cell compatibility.
TABLE 4-1
Figure BDA0001808567190000121
Example 5:
the components, preparation and performance test of the biodegradable Zn-Na series six-membered zinc alloy.
The zinc alloy contains 6 alloy elements, 2 of which are necessary alloy elements: zn and Na, and 3-6 kinds of alloying elements are further added. The chemical components of 10 embodiments of the zinc alloy are shown in table 5-1, the total amount of the added alloy elements is 0.79-1.41%, the balance is Zn, the zinc alloy belongs to low-alloying zinc alloy, and the cost is low.
The preparation and processing flow of the zinc alloy is as follows: continuous casting → hot extrusion → solution heat treatment → drawing. High-purity raw materials are used for mixing according to the content of elements in the table 5-1, the raw materials are placed in a graphite crucible of continuous casting equipment, high-purity argon is introduced for protection after vacuumizing, then the graphite crucible is heated to 780 ℃ through induction heating, and the temperature is kept for 8 minutes until the raw materials are melted and fully mixed under the stirring of electromagnetic force. Heating the graphite casting mold to 460 ℃, starting a blank drawing device to slowly draw the continuous casting slab out of the graphite casting mold, and keeping the circulating water temperature at 20 +/-1 ℃ to obtain the continuous casting slab with a bright surface, wherein zinc crystal grains are columnar crystals, and the included angle between the long axis direction of the zinc crystal grains and the length direction of the continuous casting slab is 0-10 degrees.
The hot extrusion is carried out at 190 ℃, the extrusion speed is 1mm/min, and the extrusion ratio is 16.
The solution heat treatment is carried out in a vacuum heat treatment furnace, the temperature is kept at 378 ℃ for 5-8 hours, and thenImmediately put into water with room temperature for water quenching. The relatively coarse LiZn in the alloy of the invention example in Table 5-1 was treated by the solution heat treatment4、CuZn5、Mg2Zn11Or MnZn13Partial Zn matrix is dissolved in solid solution, and the following tissue regulation and control effects are achieved: (1) li, Cu, Mg or Mn atoms are released to enter a Zn matrix to form a substitutional solid solution, so that the alloy strength is improved; (2) re-precipitation of nano-sized LiZn in the subsequent plastic working process4、CuZn5、Mg2Zn11Or MnZn13The second phase improves the comprehensive performance of the alloy.
And (3) carrying out drawing at 60-100 ℃ with the deformation of 85-96% to obtain the zinc alloy wire, wherein the average grain size of zinc grains is less than 3 mu m, and the sizes of various second phases are less than 1 mu m.
And cutting a sample from the zinc alloy wire to test electrochemical corrosion, cytotoxicity and room-temperature tensile mechanical properties. The preparation and testing of the above samples was carried out as provided in example 1.
The tensile mechanical properties at room temperature of 10 invention examples of zinc alloy in the table 5-1 are measured as follows: the yield strength is 330-500 MPa, the tensile strength is 380-700 MPa, and the elongation is 10-37%.
The electrochemical corrosion rate of 10 invention examples of zinc alloy in the table 5-1 in simulated body fluid is measured to be 0.20-0.52 mm/year.
The cytotoxicity of 10 invention zinc alloys in the table 5-1 is measured to be 0 grade or 1 grade, and the zinc alloys show good cell compatibility.
TABLE 5-1
Figure BDA0001808567190000131

Claims (8)

1. A biodegradable Zn-Na series zinc alloy is characterized by comprising the following chemical components in percentage by mass: 0.01-0.97% of Na and NaZn in the zinc alloy13The volume fraction of (A) is 0.4-40%;
one of the following 27 elements is further added into the zinc alloy, and the component ranges are respectively as follows: c: 0.003 to 3.4%, Sn: 0.01-10.2%, B: 0.003-3.1%, Ge: 0.007-7.6%, Se: 0.004-4.1%, P: 0.002-1.6%, Ag: 0.004 to 4.0%, Li: 0.002-0.82%, Cu: 0.018-6.0%, Mg: 0.005-2.0%, Ce, Pr, Nd, Sm, Ho: 0.017-4.2%, Er, Gd and Lu: 0.019-4.7%, K: 0.004-1.0%, La: 0.014 to 3.5%, Ca, Ti: 0.005-1.1%, Fe, Mn and Mo: 0.006-1.5%, Sr, Zr: 0.009-2.3%.
2. The method for producing a biodegradable Zn-Na based zinc alloy as claimed in claim 1, wherein the processing flow is divided into three types:
(1) continuous casting → hot extrusion → rolling;
(2) continuous casting → hot extrusion → solution heat treatment → drawing;
(3) continuous casting → homogenizing heat treatment → hot extrusion → rolling.
3. The method for preparing a biodegradable Zn-Na series zinc alloy as claimed in claim 2, wherein the smelting temperature of the raw materials of the continuously cast alloy is 580 to 880 ℃, the raw materials are vacuumized or protected by inert gas, the continuous casting is started after the heat preservation is carried out for 5 to 20 minutes, the casting mold is heated to 430 to 550 ℃ higher than the melting point of the zinc alloy, the continuous casting billet is cooled outside the outlet of the casting mold by using circulating water with the temperature maintained at 5 to 27 ℃, and the billet drawing speed is 0.3 to 10 cm/min.
4. The method for producing a biodegradable Zn-Na based zinc alloy as claimed in claim 2, wherein the hot extrusion is carried out at 150 to 300 ℃, the extrusion speed is 1 to 8mm/min, the extrusion ratio is 9 to 81, and the size of the second phase is refined to less than 50 μm.
5. The method for producing a biodegradable Zn-Na based zinc alloy as claimed in claim 2, wherein said rolling is carried out at room temperature to 320 ℃, the rolling speed is 0.01 to 0.1m/s, the deformation is 10 to 98%, and the crystal grain size of zinc is refined to less than 10 μm.
6. The method for producing a biodegradable Zn-Na based zinc alloy as claimed in claim 2, wherein said drawing is carried out at room temperature to 280 ℃ and the amount of deformation is 20 to 99.9%.
7. The method for producing a biodegradable Zn-Na system zinc alloy as claimed in claim 2, wherein the solution heat treatment is carried out in a vacuum or inert gas atmosphere, the temperature is maintained at 340 to 390 ℃ for 1 to 25 hours, and then water quenching is immediately carried out, 10 to 100% of relatively coarse AgZn is added3、LiZn4、CuZn5、Mg2Zn11And MnZn13The second phase is solid-dissolved in the zinc matrix, so that the degradation safety of the zinc alloy in organisms is improved.
8. The method for producing a biodegradable Zn-Na based zinc alloy as set forth in claim 2, wherein the homogenization heat treatment is carried out in 2 steps under vacuum or inert gas atmosphere, the temperature is raised to 200 to 300 ℃ at a rate of 2 to 10 ℃/min and the temperature is maintained for 1 to 4 hours, and then the temperature is raised to 350 to 380 ℃ at a rate of 1 to 5 ℃/min and the temperature is maintained for 1 to 3 hours, followed by cooling, and the cooling method comprises furnace cooling and water quenching.
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