CN114086029A - Environment-degradable heat-resistant high-strength zinc alloy and preparation method and application thereof - Google Patents
Environment-degradable heat-resistant high-strength zinc alloy and preparation method and application thereof Download PDFInfo
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- CN114086029A CN114086029A CN202111234763.9A CN202111234763A CN114086029A CN 114086029 A CN114086029 A CN 114086029A CN 202111234763 A CN202111234763 A CN 202111234763A CN 114086029 A CN114086029 A CN 114086029A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- 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
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- 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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- 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 embodiment of the invention provides an environmentally degradable heat-resistant high-strength zinc alloy, and a preparation method and application thereof, and belongs to the technical field of zinc alloys. The zinc alloy contains 0.001-30% of Ir, and other alloy elements can be further added. The zinc alloy of the present invention can be prepared by casting and thermomechanical treatment steps, as well as by 3D printing and heat treatment steps. The zinc alloy contains a fine dispersed second phase with high melting point, high hardness and good thermal stability, can effectively inhibit recrystallization and grain growth of a zinc matrix, and overcomes the defect that pure zinc is easy to soften at high temperature; meanwhile, the second phases can obviously improve the high-temperature strength, the heat resistance and the creep resistance of the zinc alloy. The zinc alloy prepared by the invention has excellent heat resistance, high-temperature strength and adjustable degradation rate, and can be applied to oil drilling and production downhole tools, hot-dip galvanized materials, construction zinc materials, die castings, zinc materials for batteries, zinc materials for printing, zinc-based alloy solder, medical implantation devices and the like.
Description
Technical Field
The invention belongs to the technical field of zinc alloy, and relates to an environment-degradable heat-resistant high-strength zinc alloy, and a preparation method and application thereof.
Background
The zinc is active in chemical property and can be degraded in the environment. In traditional application, zinc is often used as a sacrificial anode material to protect the base metal from corrosion. Compared with the traditional degradable metals of iron and magnesium, zinc has a moderate corrosion rate, and is noticed as a medical metal in recent years. However, the melting point of zinc is 419.5 ℃, the initial temperature of dynamic recrystallization is about 15 ℃, recrystallization can occur at room temperature, so that pure zinc and most zinc alloys have the problems of poor tissue thermal stability, low creep resistance and the like, and the application of the pure zinc and the zinc alloys is limited.
Patent document 1(CN111621793A) discloses a high-temperature resistant zinc alloy sacrificial anode, which comprises the following alloy components in percentage by mass: 0.5% -1.2%, In: 0.2% -0.25%, Mg: 0.5% -1.2%, Ni: 0.05-0.2%, Zr: 0.05-0.08%, Si: 0.8 to 1.2 percent and the balance of Zn.
Patent document 2(CN108118189A) discloses a high temperature resistant Ba-Os-Si zinc alloy suitable for hot chamber die casting, which comprises the following alloy components by mass percent: 0.8% -1.4%, Os: 0.4% -0.8%, Si: 5.0% -6.8%, Sc: 0.4% -0.9%, Ni: 0.8% -1.2%, Pm: 0.5 to 0.8 percent, and the balance of Zn. The tensile strength of the zinc alloy at 200 ℃ is 240-320 MPa.
Patent document 3(CN108179320A) discloses a high-temperature resistant Ba-Re-Te zinc alloy suitable for cold chamber die casting, which comprises the following alloy components in percentage by mass: 0.4% -1.2%, Re: 0.4% -0.8%, Te: 0.6% -0.8%, Ge: 2.0% -4.0%, V: 0.5% -0.8%, Pr: 0.2 to 0.4 percent of the total weight of the alloy, and the balance of Zn. The tensile strength of the zinc alloy at 200 ℃ is 220-300 MPa.
Patent document 4(CN107916351A) discloses a Li-Re-Sc-containing high-temperature-resistant high-thermal-conductivity zinc-lithium alloy, which comprises the following alloy components in percentage by mass: 0.4% -1.6%, Re: 0.2% -0.8%, Sr: 0.5% -1.2%, Al: 1.0% -2.0%, V: 0.2% -0.4%, Sc: 0.2% -0.6%, Th: 0.1% -0.2%, Nd: 0.3% -0.5%, B: 0.2 to 0.3 percent of the total weight of the alloy, and the balance of Zn. The tensile strength of the zinc alloy at room temperature is 500-650MPa, and can be maintained at about 350MPa at 150 ℃.
None of the above patents disclose the recrystallization temperature and structure stability of the designed high temperature resistant zinc alloy.
Iridium (Ir) is a face-centered cubic metal with a melting point of 2450 ℃, and due to the properties of high melting point, high hardness, high temperature resistance and the like, the service temperature of an iridium product can reach 2100-2200 ℃, and the iridium product is commonly used as a part, a high-temperature crucible and the like used for a long time in an aircraft engine. Iridium is also used for nibs, needles, balance blades, compass supports, electrical contacts, etc. Iridium is harmless to living organisms and does not react with biological tissues.
At present, no literature and patent reports about Zn-Ir series zinc alloy applied in high temperature environment and a preparation method thereof at home and abroad.
Disclosure of Invention
The invention solves the technical problem that the existing zinc alloy has poor heat resistance and high-temperature strength and cannot better meet the use requirement. The invention provides an environmentally degradable heat-resistant high-strength zinc alloy, and a preparation method and application thereof, wherein the zinc alloy has excellent heat resistance and high-temperature strength and can be used in an environment with the temperature higher than 120 ℃.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention is to provide an environmentally degradable heat-resistant high-strength zinc alloy,
the zinc alloy includes zinc and iridium; the content of iridium is 0.001-30 wt%, preferably 0.01-10 wt%, based on 100% of the total weight of the zinc alloy.
Preferably, the first and second electrodes are formed of a metal,
the zinc alloy further comprises at least one of group A elements, group B elements or group C elements;
melting point T of the group A elementsm>Preferably comprising W, Re, Os, Ta, Mo, Nb, Ru, Hf, B, Rh, V, Cr, Zr,At least one of Pt, Ti, Lu, Pd, Tm, Sc, Fe, Er, Y, Co, Ho, Ni, Si, Dy, Tb, Gd, Mn, Sm, Cu, Au, Pm and Nd;
the melting point of the B group element is more than or equal to T at 600 DEG CmAt least one of Ag, Ge, Pr, La, Yb, Ca, Ce, Sr, Ba, Al and Mg is preferably contained at the temperature of less than or equal to 1000 ℃;
the group C element includes Li.
In the present invention, T is as defined abovemThe high-melting-point alloy element with the temperature of more than or equal to 600 ℃ can be partially gathered at the defects of crystal boundary, phase boundary, twin crystal boundary, dislocation and the like, or form a high-melting-point and high-hardness thermally stable second phase which interacts with the dislocation and the interface to block the movement and the interface migration of the dislocation, inhibit the coarsening and softening of the structure at high temperature and obviously improve the heat resistance and the high-temperature strength of the zinc alloy; the high-activity element Li can be preferentially oxidized to form a compact Li-rich oxide film, so that a Zn matrix is protected, the oxidation rate of Zn is reduced, and the high-temperature performance of the Zn is improved.
Preferably, the first and second electrodes are formed of a metal,
based on the total weight of the zinc alloy as 100 percent,
the content of the group A element is 0.001-4 wt%, preferably 0.01-2 wt%;
the content of the B group element is 0.001-6 wt%, preferably 0.1-4 wt%;
the content of the C group element is 0.01-1 wt%, preferably 0.1-0.8 wt%.
The recrystallization temperature of the zinc alloy is more than or equal to 100 ℃, and is obviously higher than the recrystallization temperature of pure zinc (namely 15 ℃); the size of Zn crystal grains is less than or equal to 30 mu m, and the size of second phase particles is less than or equal to 15 mu m; keeping the temperature for 50-360 h in an air atmosphere at 50-250 ℃, wherein the coarsening degree of the structure is low, the size of Zn crystal grains is less than or equal to 40 mu m, and the size of second phase particles is less than or equal to 20 mu m.
The room temperature tensile property of the zinc alloy of the invention is as follows: the yield strength is 180MPa to 450MPa, the tensile strength is 260MPa to 650MPa, and the elongation is 5 percent to 55 percent;
the room temperature compression performance is as follows: the yield strength is 300MPa to 580MPa, the stress is 700MPa to 900MPa when the deformation is 50 percent, and the compressive strength is more than 700 MPa; the hardness value after heat preservation for 50-240 hours at 50-250 ℃ is 60-282 HV;
the high-temperature tensile property at 50-250 ℃ is as follows: the yield strength is 130MPa to 230MPa, the tensile strength is 200MPa to 410MPa, and the elongation is 25 percent to 165 percent;
the high-temperature compression performance at 50-250 ℃ is as follows: the yield strength is 100MPa to 380MPa, the stress is 230MPa to 590MPa when the deformation is 50 percent, and the compressive strength is more than 230 MPa;
the creep rate is 9 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-9～1×10-7s-1。
The degradation rate of the zinc alloy in Simulated Body Fluid (SBF) at 37 ℃, Hank's, phosphate buffer solution, normal saline and other solutions is 0.01-2 mm/y; the degradation rate in a 0.5-10% KCl or NaCl solution at 20-250 ℃ is 0.2-100 mu m/d.
The second aspect of the invention is to provide the preparation method of the environmentally degradable heat-resistant high-strength zinc alloy of the first aspect of the invention, wherein the preparation method is divided into 2;
the first preparation method comprises the steps of casting and thermomechanical treatment;
the second manufacturing method includes 3D printing and heat treatment steps.
Preferably, the first and second electrodes are formed of a metal,
in the casting process, high-purity metal with the purity of more than 99.9 percent corresponding to each element in the zinc alloy is used as a raw material, and the zinc alloy ingot is obtained by smelting for 2-8 times under the protection of vacuum or inert gas;
preferably, the adding elements of the zinc alloy are added into the zinc melt according to the sequence of melting points from low to high;
the smelting condition is that the temperature is kept at 500-800 ℃ for 2-30 min;
the deformation heat treatment is selected from at least one of homogenization heat treatment, solution heat treatment, pre-aging heat treatment, aging heat treatment and double-stage aging heat treatment and plastic deformation combined treatment mode.
Preferably, the first and second electrodes are formed of a metal,
electromagnetic stirring is further applied in the smelting process, and the frequency of the electromagnetic stirring is preferably 1000-5000 HZ;
the melting process is also added with a melt covering agent; preferably, the melt covering agent is selected from KCl, NaCl, MgCl2At least one of LiCl, rosin and borax;
the thermomechanical treatment mode comprises three modes which are respectively as follows:
(1) firstly, carrying out homogenization heat treatment, and then carrying out plastic deformation;
(2) firstly carrying out solution heat treatment and then carrying out plastic deformation;
(3) firstly carrying out solution heat treatment, then carrying out pre-aging heat treatment, then carrying out plastic deformation, then carrying out aging heat treatment, and finally carrying out plastic deformation.
Preferably, the first and second electrodes are formed of a metal,
the temperature of the homogenization heat treatment is 260-380 ℃, and the heat is preserved for 1-10 hours;
the temperature of the solution heat treatment is 320-390 ℃, and the temperature is kept for 5-60 h;
the temperature of the pre-aging heat treatment is 50-200 ℃, and the heat is preserved for 1-20 h;
the temperature of the aging heat treatment is 50-260 ℃, and the heat is preserved for 0.1-40 h;
the plastic deformation is at least 1 selected from extrusion, rolling, forging or equal channel angular extrusion;
the temperature of the plastic deformation is-100 to 350 ℃;
during extrusion, the corresponding extrusion ratio is 8-80, and the extrusion speed is 0.01-8 mms-1；
During rolling, the deformation of single-pass rolling is 2-30%, the rolling pass is 1-15, and the rolling speed is 0.1-0.8 m/s;
the forging mode is at least 1 of free forging, die forging or rotary forging, and the forging speed is 200-500 m/s.
When equal channel angular extrusion is carried out, the corresponding extrusion pass is 2-18, and the extrusion speed is 0.01-10 mm s-1The extrusion path is A path, C path, B pathARoute, BCAt least one of the paths.
The path A is directly subjected to the next extrusion process without rotation after the blank is extruded for the 1 st time;
the path C is that after the blank is extruded each time, the blank is rotated 180 degrees and enters the next extrusion process;
BAthe path is that after the 1 st extrusion of the blank, the 2 nd extrusion rotates the blank by 90 degrees, and rotates the blank by 90 degrees in the reverse direction before the 3 rd extrusion, and rotates the blank by 90 degrees in the reverse direction again for the 4 th extrusion, and so on;
BCthe path is that after each extrusion of the blank, the blank is rotated by 90 degrees along the same direction to enter the next extrusion process.
In the invention, if cooling is needed after heat treatment, the existing conventional cooling mode can be adopted, and the cooling mode can be any 1 of air cooling, furnace cooling, water quenching and oil quenching.
Preferably, the first and second electrodes are formed of a metal,
the raw material for 3D printing is spherical powder; the spherical powder is prepared by putting raw materials into powder making equipment according to the proportion of alloy components; the preparation method of the spherical powder is any 1 of a distillation method, a gas atomization method, a water atomization method, a plasma atomization method, a rotary electrode atomization method, a rotary disc atomization method, a hydrogenation-dehydrogenation method, a metal thermal reduction method, a metal vapor condensation method, a molten salt precipitation method and an aqueous solution electrolysis method;
the sphericity of the spherical powder is more than 0.9, the fluidity (the time required for 50g of powder to flow) is more than 15s, and the average grain diameter is less than or equal to 300 mu m;
when the laser for 3D printing is used as a heat source, the laser power is 50-2000W, the diameter of a light spot is 30-220 micrometers, the scanning distance is 30-380 micrometers, the scanning speed is 60-1600 mm/s, and the thickness of a powder spreading layer is 10-260 micrometers; in order to avoid sample oxidation and system pollution, inert gas is introduced into the 3D printing forming chamber until the oxygen content is less than or equal to 0.01 percent; the inert gas is 1 or more of helium (He), neon (Ne), argon (Ar), krypton (Kr) and xenon (Xe);
when the high-energy electron beam for 3D printing is used as a heat source, the power is 0.2-10 KW, the beam spot diameter is 100-500 mu m, the scanning interval is 0.1-1 mm, the scanning speed is 2-10 m/s, and the powder spreading layer thickness is 0.1-0.7 mm; the 3D printing forming chamber is in high vacuum with the vacuum degree less than or equal to 10-2Pa。
Preferably, the first and second electrodes are formed of a metal,
the heat treatment in the second preparation method comprises at least one of aging heat treatment or dual-stage aging heat treatment; preferably, the temperature of the aging heat treatment is 50-180 ℃, and the heat preservation time is 5 min-25 h;
the first stage aging heat treatment temperature of the two-stage aging heat treatment is 50-100 ℃, the heat preservation time is 5 min-10 h, the second stage aging heat treatment temperature is 120-160 ℃, and the heat preservation time is 5 min-20 h. Cooling after heat treatment; the cooling mode is any 1 of air cooling, furnace cooling, water quenching and oil quenching.
The third aspect of the invention provides the application of the zinc alloy of the first aspect of the invention in heat-resistant high-strength materials. The zinc alloy is suitable for preparing soluble bridge plugs, soluble ball seats, soluble fracturing balls, soluble oil pipes and zinc alloy die castings such as bearings, moulds, plate-shell parts, wear-resistant and shock-absorbing parts, hot-dip galvanized materials, mechanical galvanized materials, construction galvanized materials, battery zinc materials, printing zinc materials, zinc-based alloy brazing filler metal, heart coronary artery and other vascular stents, ligament repair bone nails, intestinal anastomats and the like for petroleum drilling and production.
Compared with the prior art, the invention at least has the following characteristics and advantages:
1. the zinc alloy contains a fine dispersed second phase with high melting point, high hardness and good thermal stability, can effectively inhibit recrystallization and grain growth of a zinc matrix, and overcomes the defect that pure zinc is easy to soften at high temperature; meanwhile, the second phases can obviously improve the high-temperature strength, the heat resistance and the creep resistance of the zinc alloy.
2. The recrystallization temperature of the zinc alloy is more than or equal to 100 ℃, and is obviously higher than the recrystallization temperature of pure zinc by 15 ℃.
3. The tensile strength of the zinc alloy at 250 ℃ is 200 MPa-300 MPa, and the tensile strength of pure zinc at the temperature is only 45 MPa-60 MPa; the creep rate of the zinc alloy is 9 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-9～1×10-7s-1The microhardness value after heat preservation for 50-240 hours at 50-250 ℃ is 60-282 HV, and the heat resistance and the high-temperature strength are excellent.
4. The degradation rate of the zinc alloy in a 0.5-10% KCl or NaCl solution at 20-250 ℃ is 0.2-100 mu m/d.
5. The preparation method provided by the invention is suitable for industrial popularization.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a zinc grain structure diagram of the zinc alloy 24 prepared in example 24 of the present invention at 65 ℃ for 96 h. (wherein, 1 means the maximum Zn grain size of 34um)
FIG. 2 is a second phase structure diagram of the zinc alloy 24 prepared in example 24 of the present invention at 65 ℃ for 96 h. (wherein, 2 means the largest particle, size of 2.8um)
FIG. 3 is a bar graph of the age hardness change at 65 ℃ for the zinc alloy 24 prepared in example 24 of the present invention.
Fig. 4 is a bar graph of tensile mechanical properties of the zinc alloy 24 prepared in example 24 of the present invention at 65 ℃.
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.
The test method comprises the following steps:
and (3) carrying out recrystallization temperature, room-temperature tensile and compression mechanical properties, high-temperature tensile and compression mechanical properties and creep property tests on the zinc alloy.
Wherein, the recrystallization temperature of the alloy is evaluated by combining a gold phase method and a hardness method;
evaluating the tensile mechanical property at room temperature according to the national standard GB/T228.1-2010;
evaluating the compression mechanical property at room temperature according to the national standard GB/T7314-2017;
evaluating the high-temperature tensile mechanical property according to the national standard GB/T4338-2006;
evaluating the high-temperature compression mechanical property according to the aviation industry standard HB 7571-1997;
creep performance was evaluated according to the national standard GB/T38822-2020.
Examples 1 to 13
The components, preparation and performance test of the degradable heat-resistant high-strength Zn-Ir series binary zinc alloy.
The chemical compositions of 13 examples of the degradable heat-resistant high-strength zinc alloy are shown in table 1-1. The preparation and processing flow of the zinc alloy is as follows: casting → homogenizing heat treatment → equal channel angular pressing.
Casting with purity of more than 99.9% and single particle volume of less than 8mm3The high-purity metals Zn and Ir are used as raw materials, the materials are mixed according to alloy components of the embodiment shown in the table 1-1, and the materials are repeatedly smelted for 2 times by an induction heating furnace under the protection of argon to obtain Zn-Ir series zinc alloy cast ingots; the smelting temperature is 800 ℃, and the smelting time is 10 min.
Homogenizing and heat treating at 380 deg.C for 10 hr, and cooling.
Extruding at 200 deg.C at an equal channel angle for 8 passes at an extrusion speed of 10mms-1The extrusion ratio was 26, and the extrusion path was the C path.
Observing the structure of the zinc alloy in an equal channel angular pressing state by using a metallographic microscope and a Scanning Electron Microscope (SEM), and measuring that the size of Zn crystal grains is less than or equal to 25 mu m and the size of second phase particles is less than or equal to 12 mu m; the temperature is kept for 360 hours in the air atmosphere of 100 ℃, the coarsening degree of the structure is low, the size of Zn crystal grains is less than or equal to 28 mu m, and the size of second phase particles is less than or equal to 14 mu m.
The recrystallization temperature of the zinc alloy of the example in Table 1-1 was measured to be 100 ℃ to 160 ℃. The recrystallization temperature of the pure zinc prepared by the same method is 15-26 ℃, and the addition of Ir can obviously improve the recrystallization temperature of zinc.
The room temperature tensile properties of the zinc alloy of the example in Table 1-1 were measured as follows: the yield strength is 180MPa to 250MPa, the tensile strength is 260MPa to 320MPa, and the elongation is 9 percent to 35 percent;
the room temperature compression performance is as follows: the yield strength is 300MPa to 420MPa, the stress is 720MPa to 800MPa when the compressive deformation is 50 percent, and the compressive strength is more than 720 MPa.
The pure zinc prepared by the same method has the room temperature tensile property as follows: the yield strength is 60MPa to 130MPa, the tensile strength is 140MPa to 160MPa, and the elongation is 5 percent to 15 percent;
the room temperature compression performance is as follows: the yield strength is 80MPa to 150MPa, the stress is 300MPa to 450MPa when the compressive deformation is 50 percent, and the compressive strength is more than 300 MPa. Therefore, the addition of Ir can obviously improve the room-temperature mechanical property of pure zinc and provides a good foundation for improving the high-temperature mechanical property of zinc alloy.
The microhardness value of the zinc alloy in the embodiment in the table 1-1 after heat preservation at 50-250 ℃ for 50-240 hours is measured to be 60-220 HV.
The high-temperature tensile property at 50-250 ℃ is as follows: yield strength is 130MPa to 200MPa, tensile strength is 200MPa to 280MPa, and elongation is 35 percent to 105 percent;
the high-temperature compression performance at 50-250 ℃ is as follows: the yield strength is 100MPa to 190MPa, the stress is 250MPa to 390MPa when the compressive deformation is 50 percent, and the compressive strength is more than 250 MPa.
The creep rate is 9 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-9～8×10-8s-1。
The pure zinc prepared by the same method has the following high-temperature tensile properties at 50-250 ℃: the yield strength is 35MPa to 80MPa, the tensile strength is 45MPa to 100MPa, and the elongation is 25 percent to 55 percent; therefore, the high-temperature mechanical property of the zinc can be obviously improved by adding the Ir.
The degradation rate of the zinc alloy of all the examples in the table 1-1 in an SBF solution at 37 ℃ is measured to be 0.01-0.2 mm/y; the degradation rate in 3.5% NaCl solution at 25 deg.C is 0.2-5 μm/d.
The properties of some of the preferred example zinc alloys and the comparative example pure zinc are shown in tables 1-2.
TABLE 1-1
Tables 1 to 2
Examples 14 to 23
The components, preparation and performance test of the degradable heat-resistant high-strength Zn-Ir ternary zinc alloy.
The chemical compositions of 10 examples of the degradable heat-resistant high-strength zinc alloy are shown in table 2-1. The preparation and processing flow of the zinc alloy is as follows: 3D printing → two-stage aging heat treatment.
The compositions of the alloy of the example shown in Table 2-1 were mixed to prepare spherical powder for 3D printing by gas atomization, the sphericity of the powder was 1.0 to 1.2, the fluidity (the time required for 50g of the powder to flow) was 16 to 20s, and the average particle diameter was 300. mu.m. The 3D printing is a selective laser melting technology based on a high-energy density heat source, the laser power is 200W, the diameter of a light spot is 80 micrometers, the scanning distance is 80 micrometers, the scanning speed is 100mm/s, the thickness of a powder spreading layer is 60 micrometers, and in order to avoid sample oxidation and system pollution, argon gas is introduced into a forming chamber until the oxygen content is 0.01%.
The two-stage aging heat treatment is carried out, wherein the temperature of the first-stage aging heat treatment is 100 ℃, the temperature is kept for 5-30 min, then water cooling is carried out, the temperature of the second-stage aging heat treatment is 160 ℃, the temperature is kept for 30 min-1 h, and then water cooling is carried out.
The size of Zn crystal grains in a two-stage aging heat treatment state after 3D printing is less than or equal to 20 microns, and the size of second-phase particles is less than or equal to 10 microns; the temperature is kept for 360 hours in 150 ℃ air atmosphere, the coarsening degree of the structure is low, the size of Zn crystal grains is less than or equal to 23 mu m, and the size of second phase particles is less than or equal to 12 mu m.
The recrystallization temperature, room temperature tensile and compressive mechanical properties, high temperature tensile and compressive mechanical properties and creep properties of the zinc alloy in the two-stage aged heat treated state after 3D printing were evaluated with reference to the relevant national standards in example 1.
The recrystallization temperature of the zinc alloy of all examples in Table 2-1 was measured to be 120 ℃ to 190 ℃. The recrystallization temperature of the pure zinc prepared by the same method is 15-25 ℃, and the addition of Ir can obviously improve the recrystallization temperature of zinc.
The room temperature tensile properties of all the example zinc alloys in table 2-1 were measured as: the yield strength is 220MPa to 310MPa, the tensile strength is 300MPa to 380MPa, and the elongation is 10 percent to 45 percent;
the room temperature compression performance is as follows: the yield strength is 350MPa to 480MPa, the stress is 780MPa to 860MPa when the compressive deformation is 50 percent, and the compressive strength is greater than 780 MPa.
The microhardness value of the zinc alloy of all the examples in the table 2-1 after heat preservation at 50-250 ℃ for 50-240 hours is measured to be 61-278 HV.
The high-temperature tensile property at 50-250 ℃ is as follows: the yield strength is 140MPa to 210MPa, the tensile strength is 250MPa to 390MPa, and the elongation is 46 percent to 145 percent;
the high-temperature compression performance at 50-250 ℃ is as follows: the yield strength is 100MPa to 280MPa, the stress is 240MPa to 490MPa when the compressive deformation is 50 percent, and the compressive strength is more than 240 MPa.
The creep rate is 1 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-8～1×10-7s-1。
The degradation rate of the zinc alloy of all the examples in the table 2-1 in SBF at 37 ℃ is measured to be 0.03-0.4 mm/y; the degradation rate in a 3.5% KCl solution at 65 ℃ is 0.3-10 mu m/d.
The properties of some of the preferred example zinc alloys and the comparative example pure zinc are shown in tables 2-2.
TABLE 2-1
Tables 2 to 2
Examples 24 to 31
The components, preparation and performance test of the degradable heat-resistant high-strength Zn-Ir system quaternary zinc alloy.
The chemical compositions of 9 examples of the degradable heat-resistant high-strength zinc alloy are shown in table 3-1. The preparation and processing flow of the zinc alloy is as follows: casting → solution heat treatment → aging heat treatment → hot extrusion.
Said casting being carried out with a purity of more than 99.9% and a single grain volume of less than 4mm3The high-purity metal is used as a raw material, the raw material is prepared according to alloy components of an embodiment shown in a table 3-1, and the raw material is repeatedly smelted for 5 times by using an induction heating furnace under the protection of argon to obtain a Zn-Ir system quaternary zinc alloy ingot; electromagnetic stirring is applied in the smelting process, and the frequency is 5000 HZ; the smelting temperature is 760 ℃, and the smelting time is 20 min; in order to prevent the gasification caused by boiling of the Zn liquid in the smelting process, 1 or more of the following covering agents are added: KCl, NaCl, MgCl2LiCl, rosin, borax and the like.
And performing solid solution heat treatment at the temperature of 380 ℃ for 36 hours, and then performing water cooling.
The temperature of the aging heat treatment is 85 ℃, and the water cooling is carried out after the heat preservation is carried out for 5 hours.
The hot extrusion is carried out at the temperature of 300 ℃ and the extrusion speed of 3mms-1The extrusion ratio was 20.
The size of the hot extrusion Zn crystal grain is less than or equal to 29 mu m, the size of the second phase particle is less than or equal to 11 mu m, the heat preservation is carried out for 60-360 hours in an air atmosphere at 65 ℃, the size of the Zn crystal grain is less than or equal to 38 mu m, and the size of the second phase particle is less than or equal to 8 mu m. The zinc grain and second phase structure patterns of the example alloy 24 at 65 ℃ for 96 hours are shown in fig. 1 and 2, respectively.
The recrystallization temperature, room temperature tensile and compressive mechanical properties, high temperature tensile and compressive mechanical properties, and creep properties of the hot-extruded zinc alloy were evaluated with reference to the relevant national standards in example 1.
The recrystallization temperature of the zinc alloy of all examples in Table 3-1 was measured to be 160 ℃ to 280 ℃. The recrystallization temperature of the pure zinc prepared by the same method is 13-25 ℃, and the addition of Ir can obviously improve the recrystallization temperature of zinc.
The room temperature tensile properties of all the example zinc alloys in Table 3-1 were measured as: the yield strength is 310MPa to 380MPa, the tensile strength is 310MPa to 580MPa, and the elongation is 12 percent to 55 percent.
The room temperature compression performance is as follows: the yield strength is 400MPa to 550MPa, the stress is 750MPa to 865MPa when the compressive deformation is 50 percent, and the compressive strength is more than 750 MPa.
The microhardness value of the zinc alloy of all the examples in the table 3-1 after heat preservation at 50-250 ℃ for 50-240 hours is measured to be 61-275 HV.
The high-temperature tensile property at 50-250 ℃ is as follows: the yield strength is 130MPa to 230MPa, the tensile strength is 250MPa to 400MPa, and the elongation is 26 percent to 138 percent.
The high-temperature compression performance at 50-250 ℃ is as follows: the yield strength is 130MPa to 260MPa, the stress is 310MPa to 430MPa when the compressive deformation is 50 percent, and the compressive strength is more than 310 MPa.
The creep rate is 9 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-9～7×10-8s-1。
The age hardness and tensile mechanical properties of the example alloy 24 at 65 ℃ are shown in figures 3 and 4, respectively.
The degradation rate of the zinc alloy of all the examples in the table 3-1 in a phosphate buffer solution at 37 ℃ is measured to be 0.05-0.6 mm/y; the degradation rate in 3.5% NaCl solution at 120 ℃ is 0.8-20 μm/d.
The properties of some of the preferred example zinc alloys and the comparative example pure zinc are shown in table 3-2.
TABLE 3-1
| Examples | Zinc alloy | Alloy composition |
| Example 24 | Alloy 24 | Zn-0.003Ir-0.4Mn-0.01Fe |
| Example 25 | |
Zn-0.01Ir-1Li-0.07Y |
| Example 26 | Alloy 26 | Zn-2.3Ir-1.1Nd-0.1Ba |
| Example 27 | Alloy 27 | Zn-4.8Ir-3.7Cu-0.2Fe |
| Example 28 | Alloy 28 | Zn-8Ir-0.6Ta-3Mg |
| Example 29 | |
Zn-13Ir-6Al-3Ca |
| Example 30 | |
Zn-18Ir-1.6Co-0.8Pr |
| Example 31 | Alloy 31 | Zn-24Ir-2Mn-6Sr |
TABLE 3-2
Examples 32 to 40
Degradable heat-resistant high-strength Zn-Ir quinary zinc alloy components, preparation and performance test.
The chemical compositions of 9 examples of the degradable heat-resistant high-strength zinc alloy are shown in table 4-1. The preparation and processing flow of the zinc alloy is as follows: casting → solution heat treatment → preaging heat treatment → cold forging → aging heat treatment.
Said casting being carried out with a purity of more than 99.9% and a single grain volume of less than 2mm3The high-purity metal of (2) is used as a raw material, the raw material is prepared according to alloy components of an embodiment shown in the table 4-1, and the Zn-Ir series quinary zinc alloy ingot is obtained by repeatedly smelting for 8 times by using an induction heating furnace under the protection of helium. Electromagnetic stirring is applied in the smelting process, the frequency is 5000HZ, the smelting temperature is 800 ℃, and the smelting time is 30 min. In order to prevent the Zn liquid from boiling and gasifying in the smelting process, a covering agent NaCl is added.
And performing solid solution heat treatment at the temperature of 390 ℃, and performing water cooling after heat preservation for 36 hours.
The pre-aging heat treatment is carried out at the temperature of 100 ℃, and water cooling is carried out after heat preservation is carried out for 10 hours; the aging heat treatment temperature is 120 ℃, and the water cooling is carried out after the heat preservation for 20 hours.
The cold forging is carried out at the temperature of 25 ℃, the forging mode is rotary forging, and the forging rate is 300ms-1。
The size of Zn crystal grains in an aging heat treatment state after forging is less than or equal to 26 microns, the size of second phase particles is less than or equal to 9 microns, the heat preservation is carried out for 360 hours at the temperature of 250 ℃ in an air atmosphere, the coarsening degree of the structure is low, the size of the Zn crystal grains is less than or equal to 32 microns, and the size of the second phase particles is less than or equal to 14 microns.
The zinc alloy in the post-forging aged heat-treated state was evaluated for recrystallization temperature, room-temperature tensile and compressive mechanical properties, high-temperature tensile and compressive mechanical properties, and creep properties with reference to the relevant national standards in example 1.
The recrystallization temperatures of the zinc alloys of all examples in Table 4-1 were measured to be 200 ℃ to 310 ℃. The recrystallization temperature of the pure zinc prepared by the same method is 13-27 ℃, and the addition of Ir can obviously improve the recrystallization temperature of zinc.
The room temperature tensile properties of all the example zinc alloys in Table 4-1 were measured as: the yield strength is 320MPa to 410MPa, the tensile strength is 330MPa to 530MPa, and the elongation is 18 percent to 55 percent.
The room temperature compression performance is as follows: the yield strength is 440MPa to 570MPa, the stress is 780MPa to 870MPa when the compression deformation is 50 percent, and the compressive strength is greater than 780 MPa.
The microhardness of the zinc alloy of all the examples in the table 4-1 after heat preservation at 50-250 ℃ for 50-240 hours is measured to be 66-281 HV.
The high-temperature tensile property at 50-250 ℃ is as follows: the yield strength is 150MPa to 220MPa, the tensile strength is 280MPa to 410MPa, and the elongation is 46 percent to 165 percent.
The high-temperature compression performance at 50-250 ℃ is as follows: the yield strength is 150MPa to 290MPa, the stress is 340MPa to 450MPa when the compressive deformation is 50 percent, and the compressive strength is more than 340 MPa.
The creep rate is 9 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-9～3×10-8s-1。
The degradation rate of the zinc alloy of all the examples in the table 4-1 in physiological saline at 37 ℃ is measured to be 0.07-0.9 mm/y; the degradation rate in a 6.5% KCl solution at 200 ℃ is 1.6-60 mu m/d.
The properties of some of the preferred example zinc alloys and the comparative example pure zinc are shown in table 4-2.
TABLE 4-1
| Examples | Zinc alloy | Alloy composition |
| Example 32 | Alloy 32 | Zn-0.1Ir-0.2Zr-0.1Ti-0.5Si |
| Example 33 | Alloy 33 | Zn-1.3Ir-3.3Al-0.2Sc-0.8Ba |
| Example 34 | Alloy 34 | Zn-2.9Ir-0.8Mn-0.2Ca-3.5Mg |
| Example 35 | Alloy 35 | Zn-3.3Ir-0.3Ti-0.1W-0.8Ba |
| Example 36 | Alloy 36 | Zn-4.7Ir-0.7Lu-2.5Cu-0.2Tm |
| Example 37 | Alloy 37 | Zn-7.9Ir-0.6W-5Er-0.5Pd |
| Example 38 | Alloy 38 | Zn-9.4Ir-2.8Sc-3.6Lu-2.5Zr |
| Example 39 | Alloy 39 | Zn-16.9Ir-1.6Tb-5.3Pd-2.2Ti |
| Example 40 | |
Zn-24.5Ir-2.0Zr-1.5Er-0.9Sc |
TABLE 4-2
Examples 41 to 47
The components, preparation and performance test of the degradable heat-resistant high-strength Zn-Ir multi-element zinc alloy.
The chemical compositions of 7 examples of the degradable heat-resistant high-strength zinc alloy are shown in table 5-1. The preparation and processing flow of the zinc alloy is as follows: casting → solution heat treatment → hot rolling → cold rolling.
Said casting being carried out with a purity of more than 99.9% and a single grain volume of less than 6mm3The high-purity metal is used as a raw material, the raw material is prepared according to alloy components of an embodiment shown in a table 5-1, and the raw material is repeatedly smelted for 3 times by using an induction heating furnace under the protection of argon to obtain a Zn-Ir series ternary zinc alloy ingot; the smelting temperature is 800 ℃, and the smelting time is 15 min.
And performing solid solution heat treatment at 380 ℃, and performing water cooling after heat preservation for 30 hours.
The hot rolling is carried out at the temperature of 320 ℃, the deformation of single-pass rolling is 9 percent, the rolling pass is 5, and the rolling speed is 0.8ms-1。
The cold rolling is carried out at the temperature of 25 ℃, the deformation of single-pass rolling is 5 percent, the rolling pass is 8, and the rolling speed is 0.5ms-1。
The size of the rolled Zn crystal grains is less than or equal to 21 mu m, the size of the second phase particles is less than or equal to 10 mu m, the heat preservation is carried out for 360 hours at the temperature of 200 ℃ in the air atmosphere, the coarsening degree of the structure is low, the size of the Zn crystal grains is less than or equal to 25 mu m, and the size of the second phase particles is less than or equal to 13 mu m.
The recrystallization temperature, room temperature tensile and compressive mechanical properties, high temperature tensile and compressive mechanical properties, and creep properties of the cold rolled zinc alloy were evaluated with reference to the relevant national standards in example 1.
The recrystallization temperature of the zinc alloy of all examples in Table 5-1 was measured to be 240 ℃ to 310 ℃. The recrystallization temperature of the pure zinc prepared by the same method is 15-25 ℃, and the addition of Ir can obviously improve the recrystallization temperature of zinc.
The room temperature tensile properties of all the example zinc alloys in Table 5-1 were measured as: the yield strength is 320MPa to 450MPa, the tensile strength is 380MPa to 650MPa, and the elongation is 12 percent to 55 percent.
The room temperature compression performance is as follows: the yield strength is 550MPa to 580MPa, the stress is 790MPa to 890MPa when the compressive deformation is 50 percent, and the compressive strength is more than 790 MPa.
The microhardness value of the zinc alloy of all the examples in the table 5-1 after heat preservation at 50-250 ℃ for 50-240 h is measured to be 61-282 HV.
The high-temperature tensile property at 50-250 ℃ is as follows: the yield strength is 150MPa to 220MPa, the tensile strength is 250MPa to 410MPa, and the elongation is 46 percent to 165 percent.
The high-temperature compression performance at 50-250 ℃ is as follows: the yield strength is 100MPa to 200MPa, the stress is 230MPa to 410MPa when the compressive deformation is 50 percent, and the compressive strength is more than 230 MPa.
The creep rate is 5 multiplied by 10 under the conditions of 50-180 ℃ and 30-130 MPa-8～1×10-7s-1。
The degradation rate of the zinc alloy of all the examples in the table 5-1 in the Hank's solution at 37 ℃ is measured to be 0.03-0.4 mm/y; the degradation rate in a 10% KCl solution at 250 ℃ is 6-100 mu m/d.
The properties of some of the preferred example zinc alloys and the comparative example pure zinc are shown in table 5-2.
TABLE 5-1
TABLE 5-2
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 (10)
1. An environment degradable heat-resistant high-strength zinc alloy is characterized in that,
the zinc alloy includes zinc and iridium; the content of iridium is 0.001-30 wt%, preferably 0.01-10 wt%, based on 100% of the total weight of the zinc alloy.
2. The environmentally degradable heat resistant high strength zinc alloy of claim 1,
the zinc alloy further comprises at least one of group A elements, group B elements or group C elements;
melting point T of the group A elementsm>At 1000 ℃, preferably comprising at least one of W, Re, Os, Ta, Mo, Nb, Ru, Hf, B, Rh, V, Cr, Zr, Pt, Ti, Lu, Pd, Tm, Sc, Fe, Er, Y, Co, Ho, Ni, Si, Dy, Tb, Gd, Mn, Sm, Cu, Au, Pm, Nd;
the melting point of the B group element is more than or equal to T at 600 DEG CmAt least one of Ag, Ge, Pr, La, Yb, Ca, Ce, Sr, Ba, Al and Mg is preferably contained at the temperature of less than or equal to 1000 ℃;
the group C element includes Li.
3. The environmentally degradable heat resistant high strength zinc alloy of claim 2,
based on the total weight of the zinc alloy as 100 percent,
the content of the group A element is 0.001-4 wt%, preferably 0.01-2 wt%;
the content of the B group element is 0.001-6 wt%, preferably 0.1-4 wt%;
the content of the C group element is 0.01-1 wt%, preferably 0.1-0.8 wt%.
4. The method for preparing the environmentally degradable heat-resistant high-strength zinc alloy according to any one of claims 1 to 3,
the preparation method is divided into 2 types;
the first preparation method comprises the steps of casting and thermomechanical treatment;
the second manufacturing method includes 3D printing and heat treatment steps.
5. The method for preparing the environmentally degradable heat-resistant high-strength zinc alloy according to claim 4,
in the casting process, high-purity metal with the purity of more than 99.9 percent corresponding to each element in the zinc alloy is used as a raw material, and the zinc alloy ingot is obtained by smelting for 2-8 times under the protection of vacuum or inert gas;
preferably, the adding elements of the zinc alloy are added into the zinc melt according to the sequence of melting points from low to high;
the smelting conditions are as follows: preserving the heat for 2-30 min at 500-800 ℃;
the deformation heat treatment is selected from at least one of homogenization heat treatment, solution heat treatment, pre-aging heat treatment, aging heat treatment and double-stage aging heat treatment and plastic deformation combined treatment mode.
6. The method for preparing the environmentally degradable heat-resistant high-strength zinc alloy according to claim 5,
electromagnetic stirring is further applied in the smelting process, and the frequency of the electromagnetic stirring is preferably 1000-5000 HZ;
the melting process is also added with a melt covering agent; preferably, the melt covering agent is selected from KCl, NaCl, MgCl2At least one of LiCl, rosin and borax;
the thermomechanical treatment mode comprises three modes which are respectively as follows:
(1) firstly, carrying out homogenization heat treatment, and then carrying out plastic deformation;
(2) firstly carrying out solution heat treatment and then carrying out plastic deformation;
(3) firstly carrying out solution heat treatment, then carrying out pre-aging heat treatment, then carrying out plastic deformation, then carrying out aging heat treatment, and finally carrying out plastic deformation.
7. The method for preparing the environmentally degradable heat-resistant high-strength zinc alloy according to claim 6,
the temperature of the homogenization heat treatment is 260-380 ℃, and the heat is preserved for 1-10 hours;
the temperature of the solution heat treatment is 320-390 ℃, and the temperature is kept for 5-60 h;
the temperature of the pre-aging heat treatment is 50-200 ℃, and the heat is preserved for 1-20 h;
the temperature of the aging heat treatment is 50-260 ℃, and the heat is preserved for 0.1-40 h;
the plastic deformation is at least 1 selected from extrusion, rolling, forging or equal channel angular extrusion;
the temperature of the plastic deformation is-100 to 350 ℃;
during extrusion, the corresponding extrusion ratio is 8-80, and the extrusion speed is 0.01-8 mm s-1；
During rolling, the deformation of single-pass rolling is 2-30%, the rolling pass is 1-15, and the rolling speed is 0.1-0.8 m/s;
the forging mode is at least 1 of free forging, die forging or rotary forging, and the forging speed is 200-500 m/s;
when equal channel angular extrusion is carried out, the corresponding extrusion pass is 2-18, and the extrusion speed is 0.01-10 mm s-1The extrusion path is A path, C path, B pathARoute, BCAt least one of the paths.
8. The method for preparing the environmentally degradable heat-resistant high-strength zinc alloy according to claim 4,
the raw material for 3D printing is spherical powder;
the sphericity of the spherical powder is more than 0.9, the fluidity is more than 15s, and the average grain diameter is less than or equal to 300 mu m;
when the laser for 3D printing is used as a heat source, the laser power is 50-2000W, the diameter of a light spot is 30-220 micrometers, the scanning distance is 30-380 micrometers, the scanning speed is 60-1600 mm/s, and the thickness of a powder spreading layer is 10-260 micrometers; in order to avoid sample oxidation and system pollution, inert gas is introduced into the 3D printing forming chamber until the oxygen content is less than or equal to 0.01 percent;
when the high-energy electron beam for 3D printing is used as a heat source, the power is 0.2-10 KW, the beam spot diameter is 100-500 mu m, the scanning interval is 0.1-1 mm, the scanning speed is 2-10 m/s, and the powder spreading layer thickness is 0.1-0.7 mm; the 3D printing forming chamber is in high vacuum with the vacuum degree less than or equal to 10-2Pa。
9. The method for preparing the environmentally degradable heat-resistant high-strength zinc alloy according to claim 8,
the heat treatment in the second preparation method comprises at least one of aging heat treatment or dual-stage aging heat treatment; preferably, the temperature of the aging heat treatment is 50-180 ℃, and the heat preservation time is 5 min-25 h;
the first stage aging heat treatment temperature of the two-stage aging heat treatment is 50-100 ℃, the heat preservation time is 5 min-10 h, the second stage aging heat treatment temperature is 120-160 ℃, and the heat preservation time is 5 min-20 h.
10. Use of a zinc alloy according to any one of claims 1 to 3 in heat-resistant high-strength materials.
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