CN117821819A - High-strength and high-toughness corrosion-resistant magnesium alloy and preparation method thereof - Google Patents
High-strength and high-toughness corrosion-resistant magnesium alloy and preparation method thereof Download PDFInfo
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- 238000001125 extrusion Methods 0.000 claims abstract description 55
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Abstract
The invention provides a high-strength and high-toughness corrosion-resistant magnesium alloy and a preparation method thereof, and relates to the technical field of metal materials, wherein the alloy comprises the following components in percentage by mass: zn:0.8-2.0%, sn:0.1-1.0%, ca:0.1-1.0%, mn:0-0.5%, and the balance of Mg and unavoidable impurities. The magnesium alloy prepared by the invention has excellent mechanical property and corrosion resistance, the used alloying elements are less than 4 percent and are all non-rare earth elements, and the preparation mode is simple homogenization heat treatment and extrusion, so that the alloy has low cost and easy preparation, and is further suitable for being used as a material for regenerating bone tissues.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a high-strength and high-toughness corrosion-resistant magnesium alloy and a preparation method thereof.
Background
Magnesium alloy is favored in light weight, energy saving, environmental protection and other aspects because of its advantages such as low density, high specific strength, better recyclability and the like. At present, magnesium alloy is widely applied to the fields of structural materials, functional materials, biological materials and the like, and is the lightest metal material in the current structural materials. In addition, because the magnesium alloy material has the advantages of excellent damping and shock absorption, electromagnetic shielding property, heat conduction and electric conductivity, free cutting processing and the like, the magnesium alloy has been gradually and widely applied to the fields of aerospace parts, transportation carrier structural members, 3C product shells and the like at present, has great application potential in the aspect of light miniaturization of devices, and is considered to be an excellent light high-strength engineering structural material capable of replacing steel and aluminum alloy.
However, the magnesium alloy has the defects of poor mechanical properties and corrosion resistance at room temperature, and is a main reason for preventing the magnesium alloy from being applied on a large scale. In the current art, researchers have generally introduced a second phase into magnesium alloys by way of alloying to enhance the mechanical properties of the magnesium alloys. However, the potential difference between the α -Mg matrix and the second phase causes galvanic corrosion to occur, and the corrosion resistance tends to be rather low. This is the contradiction between the development of magnesium alloy in the current industrial application. Currently, the dominant commercial magnesium alloy systems, for example: AZ series, ZK60, WE43 and the like, and the corrosion resistance and the mechanical properties of the AZ series, ZK60, WE43 and the like are required to be further improved.
Therefore, a magnesium alloy system with high corrosion resistance and mechanical property and a preparation method thereof are urgently needed at present.
Disclosure of Invention
The invention aims to provide a high-strength and high-toughness corrosion-resistant magnesium alloy and a preparation method thereof, so as to solve the technical problems of insufficient mechanical property, poor corrosion resistance and the like of the magnesium alloy in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a high-strength and high-toughness corrosion-resistant magnesium alloy, which comprises the following components in percentage by mass: zn:0.8-2.0%, sn:0.1-1.0%, ca:0.1-1.0%, mn:0-0.5%, and the balance Mg and unavoidable impurities, wherein the total content of Zn, sn, ca and Mn in the magnesium alloy is lower than 4%.
Further, the total content of Zn, sn, ca and Mn in the magnesium alloy is not higher than 3% by mass percent;
or the content of Zn in the magnesium alloy is 0.1-1.2%; the content of Sn is 0.1-0.4%; the content of Ca is 0.1-0.4%; mn content is 0-0.5%.
Further, in the magnesium alloy, the atomic ratio of Sn element to Ca element is 1: (1-6).
Further, the microstructure of the magnesium alloy comprises alpha-Mg, caMgSn, mg 2 At least two of Ca and beta-Mn.
Further, the yield strength of the magnesium alloy is 216 MPa-368 MPa, the tensile strength is 282 MPa-374 MPa, the elongation is 9% -22%, and the weight loss degradation rate is 0.20-0.25 mm/y.
The invention also provides a preparation method of the high-strength and high-toughness corrosion-resistant magnesium alloy, which comprises the following steps:
s1, preparing materials: polishing and cleaning the raw materials of the high-strength and high-toughness corrosion-resistant magnesium alloy respectively;
s2, melting: melting the cleaned raw materials to obtain a molten mixture;
s3, casting and forming: standing the molten mixture, pouring the mixture into a preheated mold, solidifying and demolding to obtain a magnesium alloy cast ingot;
s4, heat treatment: homogenizing heat treatment is carried out on the magnesium alloy cast ingot, and then cooling is carried out to room temperature;
s5, turning: turning the ingot blank after heat treatment to remove oxide skin and obtain an extrusion blank;
s6, extruding: and preheating the extrusion blank subjected to turning and peeling, and performing hot extrusion processing to obtain the high-strength and high-toughness corrosion-resistant magnesium alloy.
Further, in step S1, the raw materials of the high-strength and high-toughness corrosion-resistant magnesium alloy include magnesium, zinc, tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy.
Further, in the step S3, the casting temperature is 680-720 ℃;
and/or, the preheating mould is a graphite mould;
and/or the temperature of the preheating mould is 200-300 ℃.
Further, in step S4, the homogenizing heat treatment is a two-stage heat treatment process, including:
the temperature of the first-stage soaking heat treatment is 300-350 ℃, preferably 350 ℃;
the second-stage soaking heat treatment temperature is 480-520 ℃, preferably 500 ℃;
and/or the time of the heat treatment of the first stage and the second stage is 8h-12h, preferably 12h.
Further, in step S6, the process conditions of the hot extrusion are as follows:
the hot extrusion temperature is 260-350 ℃, the extrusion speed is 0.1-0.5 mm/s, and the extrusion ratio is 12:1-25:1, a step of;
and/or, the conditions of the preheating treatment include:
the preheating temperature is 260-350 ℃ and the preheating time is 15-30 min.
The high-strength high-toughness corrosion-resistant magnesium alloy and the preparation method thereof have the beneficial effects that:
1. the magnesium alloy obtained by the preparation method has excellent mechanical property and corrosion resistance, the used alloying elements are less than 4 percent and are all non-rare earth elements, and the preparation mode is simple homogenization heat treatment and extrusion, so that the alloy has low cost and easy preparation, and is further suitable for being used as a bone tissue regeneration material.
2. The coordination effect of simultaneous addition of Zn, sn, ca and Mn with low content optimizes the potential difference between the alpha-Mg matrix and the second phase, and reduces the occurrence of galvanic corrosion. The addition of Sn element results in SnO and SnO in the corrosion products 2 In addition, because of the high hydrogen evolution overpotential of Sn element, the hydrogen evolution reaction is effectively inhibited, and the corrosion rate is reduced.
3. The particle excitation nucleation mechanism of the second phase effectively promotes the occurrence of dynamic recrystallization in the extrusion process, segregation of Zn and Ca elements at the grain boundary and numerous nano precipitated phases effectively pin the grain boundary movement, under the combined action, the grains are thinned to submicron level, the strength of the alloy is effectively improved by superfine grains and residual stress strain, and the toughness of the alloy is maintained by the microstructure of a heterogeneous grain structure.
4. The invention discloses a preparation method of high-strength and high-toughness corrosion-resistant magnesium alloy, which mainly designs and regulates the addition amount of alloy elements through a specific alloy system, optimizes alloy phases, and improves the performance of the existing magnesium alloy in a mode of matching with a hot working process and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope photograph of an alloy of Mg-1.0Zn-0.15Sn-0.3Ca-0.1Mn provided in example 1 of the present invention;
FIG. 2 is a scanning electron microscope photograph of the Mg-1.0Zn-0.1Sn-0.1Ca alloy provided in example 5 of the present invention;
FIG. 3 shows the results of mechanical property tests of the high-strength and high-toughness corrosion-resistant magnesium alloys prepared in examples 1, 2, 3, 4 and 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The process parameters for the specific conditions not noted in the examples below are generally as usual.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention.
According to a first aspect of the invention, a high-strength and high-toughness corrosion-resistant magnesium alloy is provided, which comprises the following components in percentage by mass: zn:0.8-2.0%, sn:0.1-1.0%, ca:0.1-1.0%, mn:0-0.5%, and the balance Mg and unavoidable impurities, wherein the total content of Zn, sn, ca and Mn in the magnesium alloy is lower than 4%.
Specifically, the synergistic effect of simultaneous addition of Zn, sn, ca and Mn with low content optimizes the potential difference between the alpha-Mg matrix and the second phase, reduces the occurrence of galvanic corrosion, and improves the corrosion resistance of the magnesium alloy. The addition of Sn element results in the formation of SnO and SnO in the corrosion product layer 2 The compactness of the corrosion product layer is promoted, the reaction between the matrix and external corrosion substances can be isolated or delayed, and the corrosion resistance of the magnesium alloy is effectively improved; in addition, because of the high hydrogen evolution overpotential of Sn element, the hydrogen evolution reaction is effectively inhibited, and the corrosion rate is further reduced. The addition of Mn element can refine crystal grains, raise self-corrosion potential of alloy and increase nucleation sites of corrosion-resistant products.
The particle excitation nucleation mechanism of the second phase effectively promotes the occurrence of dynamic recrystallization in the extrusion process, segregation of Zn and Ca elements at the grain boundary and effective pinning of a plurality of nano precipitated phases enable grain boundary movement, under the combined action of the Zn and Ca elements, grains can be thinned to submicron level, superfine grains and residual stress strain effectively improve the strength of the magnesium alloy, and the microstructure of a heterogeneous grain structure effectively maintains the plasticity and toughness of the alloy.
Specifically, the total amount of the additive elements is limited to less than 4% in order to maintain the corrosion resistance of the alloy, because the degradation rate of the magnesium alloy shows a rapid increase tendency with the increase of the alloying elements, thereby reducing the corrosion resistance of the magnesium alloy.
As an alternative embodiment of the present invention, the total amount of impurities is less than or equal to 0.05% by mass percent.
As an alternative embodiment of the present invention, the total content of Zn, sn, ca and Mn in the magnesium alloy is not higher than 3% (such as 1.2%, 1.5%, 1.8%, 2.0%, 2.5%, 2.8%) by mass percent;
or the content of Zn in the magnesium alloy is 0.1-1.2%; the content of Sn is 0.1-0.4%; the content of Ca is 0.1-0.4%; mn content is 0-0.5%.
As an alternative embodiment of the present invention, in the magnesium alloy, an atomic ratio of Sn element to Ca element is 1: (1-6) (e.g., 1:2, 1:3, 1:4, 1:5, etc.).
Specifically, the purpose of strictly controlling the atomic ratio of Sn and Ca is to control the atomic ratio, size and number of the CaMgSn phase, which is an important second phase in the magnesium alloy composition, so as to achieve control of alloy properties; if the temperature is higher than the above range, the CaMgSn phase is gradually coarsened, so that the plasticity of the alloy is deteriorated, the galvanic corrosion is aggravated, and the synchronous deterioration of the plasticity and the corrosion resistance is caused; if the content is less than the above range, the CaMgSn phase is not sufficiently formed, and the alloy properties are affected.
As an alternative embodiment of the invention, the microstructure of the magnesium alloy comprises alpha-Mg, caMgSn, mg 2 At least two of Ca and beta-Mn.
Specifically, the main roles of the microstructure are grain refinement and precipitation strengthening:
(1) In the hot extrusion process, the dislocation movement is pinned by a particle excitation nucleation mode, the dislocation accumulation is promoted, the recrystallization in the extrusion induction process is accelerated, the grains are refined, and the grain refinement can obviously strengthen the performance of the magnesium alloy;
(2) In the use process, the precipitation strengthening ensures that the second phase can effectively prevent dislocation movement and improve the strength.
As an alternative embodiment of the invention, the yield strength of the magnesium alloy is 216 MPa-368 MPa, the tensile strength is 282 MPa-374 MPa, the elongation is 9% -22%, and the weight loss degradation rate is 0.20-0.25 mm/y.
The mechanical property test method is tested according to GB/T228.1-2021 metal material tensile test, the design of the sample size is according to the table G.1 circular cross section proportion sample in the standard, and the strain rate is 10 ^-3 s ^-1 Three parallel samples per group. The method for testing the soaking weightlessness degradation rate is carried out according to ASMT G31 Standard Guide for Laboratory Immersion Corrosion Testing of Metals, wherein the size of the sample is 5mm multiplied by 25mm multiplied by 1.6mm, three parallel samples are arranged in each group, the soaking solution is a common simulated body fluid Hank's solution, and the ratio of the volume of the solution to the surface area of the sample is 0.20mL/mm 2 The infusion solution was refreshed every 24 hours.
According to a second aspect of the present invention, there is also provided a method for preparing the above high strength and toughness corrosion resistant magnesium alloy, comprising the steps of:
s1, preparing materials: polishing and cleaning the raw materials of the high-strength and high-toughness corrosion-resistant magnesium alloy respectively;
s2, melting: melting the cleaned raw materials to obtain a molten mixture;
s3, casting and forming: standing the molten mixture, pouring the mixture into a preheated mold, solidifying and demolding to obtain a magnesium alloy cast ingot;
s4, heat treatment: homogenizing heat treatment is carried out on the magnesium alloy cast ingot, and then cooling is carried out to room temperature;
s5, turning: turning the ingot blank after heat treatment to remove oxide skin and obtain an extrusion blank;
s6, extruding: and preheating the extrusion blank subjected to turning and peeling, and performing hot extrusion processing to obtain the high-strength and high-toughness corrosion-resistant magnesium alloy.
The magnesium alloy obtained by the preparation method has excellent mechanical property and corrosion resistance, the used alloying elements are less than 4 percent and are all non-rare earth elements, and the preparation mode is simple homogenization heat treatment and extrusion, so that the alloy has low cost and easy preparation, and is further suitable for being used as a bone tissue regeneration material.
As an alternative embodiment of the present invention, in step S1, the raw materials of the high-strength and high-toughness corrosion-resistant magnesium alloy include magnesium, zinc, tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy.
Specifically, magnesium is a high-purity magnesium ingot with a purity of 99.99wt.% or more;
zinc is pure zinc particles, and the purity of the zinc particles is more than or equal to 99.999wt.%;
tin is pure tin particles with a purity of 99.999wt.% or more;
the Mg-Ca master alloy is Mg-30wt.% Ca master alloy;
the Mg-Mn intermediate alloy is Mg-5wt.% Mn intermediate alloy.
Specifically, ca element and Mn element are added in the form of Mg-Ca and Mg-Mn intermediate alloy because the melting point of Ca element and Mn element is far higher than that of pure magnesium, and the intermediate alloy can effectively solve the problem that the high-melting-point simple substance is not easy to melt. And because Ca element is too active and difficult to store, simple substance Ca can react with oxygen in air quickly and turn black, and is converted into calcium oxide with ultrahigh melting point, and the success rate of finished cast ingots can be improved by using intermediate alloy.
As an alternative embodiment of the present invention, step S2 includes the steps of:
placing the polished raw materials into a crucible, vacuumizing to 16-30Pa, heating to 180-250deg.C (such as 190 deg.C, 200 deg.C, 210 deg.C, 220 deg.C, 230 deg.C, 240 deg.C, etc.), maintaining for 3-5 min to preheat the materials, and simultaneously N-treating 2 Purging; heating to 680-780 deg.C (700 deg.C, 720 deg.C, 740 deg.C, 760 deg.C, etc.), maintaining until the raw materials are completely melted to form molten mixture, and stopping heating.
As an alternative embodiment of the present invention, in step S3, the casting temperature is 680-720 ℃ (e.g., 690 ℃, 700 ℃, 710 ℃, etc.);
and/or, the preheating mould is a graphite mould;
and/or the temperature of the preheating mould is 200-300 ℃.
As an optional embodiment of the present invention, in step S4, the homogenizing heat treatment is a two-stage heat treatment process, including:
the first stage soaking heat treatment temperature is 300-350deg.C (such as 310 deg.C, 320 deg.C, 330 deg.C, 340 deg.C, etc.), preferably 350deg.C;
the second stage soaking heat treatment temperature is 480-520 ℃ (such as 490 ℃, 500 ℃, 510 ℃ and the like), preferably 500 ℃;
and/or the time of the heat treatment for the homogenization of the first stage and the second stage is 8h-12h (such as 9h, 10h, 11h, etc.), preferably 12h.
Specifically, the effects of the homogenization heat treatment include:
(1) The heat diffusion movement of atoms is promoted by heating, so that the segregation problem formed by the alloy in the casting stage is solved, and the hot extrusion formability of the alloy is improved;
(2) Meanwhile, the solution treatment function is realized, so that the second phase is dissolved back into the matrix, the hot extrusion molding performance of the alloy can be improved, and the hot extrusion process can be combined through the process, so that the effective second phase grain refinement is realized.
Specifically, by adopting a two-stage heat treatment process, the secondary growth of ingot crystal grains in the heat treatment process can be controlled, so that each element in the magnesium alloy is more fully dissolved back and more uniformly distributed, the density of precipitated phases after extrusion can be improved, the crystal grains are refined, and the alloy strength is effectively improved.
As an optional embodiment of the present invention, in step S6, the process conditions of the hot extrusion are as follows:
the hot extrusion temperature is 260-350 ℃ (such as 280 ℃, 300 ℃, 320 ℃, 340 ℃ and the like), the extrusion speed is 0.1mm/s-0.5mm/s (such as 0.2mm/s, 0.25mm/s, 0.3mm/s, 0.35mm/s, 0.4mm/s, 0.45mm/s and the like), and the extrusion ratio is 12:1-25:1 (e.g., 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, etc.);
and/or, the conditions of the preheating treatment include:
the preheating temperature is 260-350deg.C (such as 280 deg.C, 300 deg.C, 320 deg.C, 340 deg.C, etc.), and the preheating time is 15-30 min (such as 20min, 25min, etc.).
Specifically, the hot extrusion temperature is strictly controlled to be 260-350 ℃, and crystal grains coarsen due to the fact that the temperature is too high, the material extrusion difficulty is increased due to the fact that the temperature is too low, and rheological stress is remarkably increased only in the range of 260-350 ℃, so that crystal grain refinement is promoted.
Specifically, the extrusion speed is strictly controlled to be 0.1-0.5 mm/s, and the friction force is increased due to the fact that the extrusion speed is too high, and further the extrusion temperature is increased to coarsen grains; too low a pressing speed reduces the rheological stress and further leads to coarsening of the grains.
The present invention will be described in further detail with reference to specific examples and comparative examples.
Example 1
The high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy is prepared from magnesium alloy cast ingots, and the magnesium alloy cast ingots comprise the following components in percentage by mass: zn:1.0%, sn:0.15%, ca:0.3%, mn:0.1% of Mg and unavoidable impurities in balance; wherein the atomic ratio of Sn to Ca is 1:6.
the preparation method of the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy comprises the procedures of melting, casting forming, homogenizing heat treatment, extrusion and the like, wherein Mg element, zn element and Sn element are respectively added in the forms of pure magnesium, pure zinc and pure tin, and Ca and Mn are respectively added in the forms of Mg-Ca intermediate alloy and Mg-Mn intermediate alloy, and the specific steps are as follows:
s1, preparing materials: polishing and cleaning pure magnesium, pure zinc, pure tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy respectively;
s2, melting: vacuum pumping the hearth, heating to 180 ℃ and N 2 Purging, namely preheating the raw materials of each component in the step S1, heating to 700 ℃, preserving heat to enable the raw materials to be completely melted to form a molten mixture, and stopping heating;
s3, casting and forming: standing the molten mixture in the step S2 for a period of time to control a casting temperature, wherein the casting temperature is 700 ℃; pouring the molten mixture into a preheated graphite mould, solidifying and demoulding to obtain a magnesium alloy cast ingot;
s4, heat treatment: heating the magnesium alloy cast ingot obtained in the step S3 to 350 ℃, preserving heat for 12 hours, further heating to 500 ℃, and preserving heat for 12 hours to obtain a cast rod;
s5, turning: turning the cast rod subjected to heat treatment in the step S4, and removing oxide scales to obtain an extrusion blank;
s6, extruding: after preheating the extruded blank after turning the skin in the step S5 for 15 minutes at 300 ℃, carrying out hot extrusion processing at the same temperature, wherein the extrusion rate is 0.25mm/S, and the extrusion ratio is 16:1, obtaining the high-strength high-toughness corrosion-resistant Mg-1.0Zn-0.15Sn-0.3Ca-0.1Mn magnesium alloy.
The mechanical properties and weightlessness degradation test results of the high-strength and toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy obtained in the embodiment are as follows: tensile strength R m =354 MPa, yield strength R p0.2 349 MPa, elongation a=11.3%, degradation rate C R =0.22 mm/y, the test results are the average of three parallel results.
Fig. 1 is an SEM image after extrusion in step S6 of example 1. The microstructure of the magnesium alloy prepared in example 1 consisted mainly of α -Mg and CaMgSn phases. It can be seen that the grain structure of the extruded rod is mainly composed of ultrafine recrystallized grains and grains, the recrystallized grains are remarkably refined in size, and the average recrystallized grains are 0.87 μm in size.
Example 2
The high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy is prepared from magnesium alloy cast ingots, and the magnesium alloy cast ingots comprise the following components in percentage by mass: zn:1.0%, sn:0.15%, ca:0.3%, mn:0.1% of Mg and unavoidable impurities in balance; wherein the atomic ratio of Sn to Ca is 1:6.
the preparation method of the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy comprises the procedures of melting, casting forming, homogenizing heat treatment, extrusion and the like, wherein Mg element, zn element and Sn element are respectively added in the forms of pure magnesium, pure zinc and pure tin, and Ca and Mn are respectively added in the forms of Mg-Ca intermediate alloy and Mg-Mn intermediate alloy, and the specific steps are as follows:
s1, preparing materials: polishing and cleaning pure magnesium, pure zinc, pure tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy respectively;
s2, melting: vacuum pumping the hearth, heating to 250 ℃, and heating to N 2 Purging, preheating the raw materials of each component in the step S1, heating to 680 ℃, preserving heat to enable the raw materials to be completely melted to form a molten mixture, and stopping heating;
s3, casting and forming: standing the molten mixture in the step S2 for a period of time to control a casting temperature, wherein the casting temperature is 680 ℃; pouring the molten mixture into a preheated graphite mould, solidifying and demoulding to obtain a magnesium alloy cast ingot;
s4, heat treatment: heating the magnesium alloy cast ingot obtained in the step S3 to 350 ℃, preserving heat for 12 hours, further heating to 500 ℃, and preserving heat for 12 hours to obtain a cast rod;
s5, turning: turning the cast rod subjected to heat treatment in the step S4, and removing oxide scales to obtain an extrusion blank;
s6, extruding: preheating the extruded blank after turning the skin in the step S5 for 15 minutes at 325 ℃, and performing hot extrusion processing at the same temperature, wherein the extrusion rate is 0.25mm/S, and the extrusion ratio is 16:1, obtaining the high-strength high-toughness corrosion-resistant Mg-1.0Zn-0.15Sn-0.3Ca-0.1Mn magnesium alloy.
The mechanical properties and weightlessness degradation test results of the high-strength and toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy obtained in the embodiment are as follows: tensile strength R m =317 MPa, yield strength R p0.2 300 MPa, elongation a=15.2%, degradation rate C R =0.21 mm/y, the test results are the average of three parallel results. The present example increases the extrusion temperature, and the grain size of the magnesium alloy increases, resulting in a decrease in strength and an increase in plasticity, as compared with example 1.
Example 3
The high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy is prepared from magnesium alloy cast ingots, and the magnesium alloy cast ingots comprise the following components in percentage by mass: zn:1.0%, sn:0.15%, ca:0.3%, mn:0.1% of Mg and unavoidable impurities in balance; wherein the atomic ratio of Sn to Ca is 1:6.
the preparation method of the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy comprises the procedures of melting, casting forming, homogenizing heat treatment, extrusion and the like, wherein Mg element, zn element and Sn element are respectively added in the forms of pure magnesium, pure zinc and pure tin, and Ca and Mn are respectively added in the forms of Mg-Ca intermediate alloy and Mg-Mn intermediate alloy, and the specific steps are as follows:
s1, preparing materials: polishing and cleaning pure magnesium, pure zinc, pure tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy respectively;
s2, melting: vacuum pumping the hearth, heating to 200 ℃, and heating to N 2 Purging, namely preheating the raw materials of each component in the step S1, heating to 700 ℃, preserving heat to enable the raw materials to be completely melted to form a molten mixture, and stopping heating;
s3, casting and forming: standing the molten mixture in the step S2 for a period of time to control a casting temperature, wherein the casting temperature is 700 ℃; pouring the molten mixture into a preheated graphite mould, solidifying and demoulding to obtain a magnesium alloy cast ingot;
s4, heat treatment: heating the magnesium alloy cast ingot obtained in the step S3 to 350 ℃, preserving heat for 12 hours, further heating to 500 ℃, and preserving heat for 12 hours to obtain a cast rod;
s5, turning: turning the cast rod subjected to heat treatment in the step S4, and removing oxide scales to obtain an extrusion blank;
s6, extruding: preheating the extruded blank after turning the skin in the step S5 for 15 minutes at the temperature of 350 ℃, and carrying out hot extrusion processing at the same temperature, wherein the extrusion rate is 0.4mm/S, and the extrusion ratio is 12:1, obtaining the high-strength high-toughness corrosion-resistant Mg-1.0Zn-0.15Sn-0.3Ca-0.1Mn magnesium alloy.
The mechanical properties and weightlessness degradation test results of the high-strength and toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy obtained in the embodiment are as follows: tensile strength R m =282 MPa, yield strength R p0.2 216 MPa, elongation a=21.8%, degradation rate C R =0.20 mm/y, the test results are the average of three parallel results.
Example 4
The high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy is prepared from magnesium alloy cast ingots, and the magnesium alloy cast ingots comprise the following components in percentage by mass: zn:1.0%, sn:0.3%, ca:0.3%, mn:0.5% of Mg and unavoidable impurities in balance; wherein the atomic ratio of Sn to Ca is 1:3.
the preparation method of the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy comprises the procedures of melting, casting forming, homogenizing heat treatment, extrusion and the like, wherein Mg element, zn element and Sn element are respectively added in the forms of pure magnesium, pure zinc and pure tin, and Ca and Mn are respectively added in the forms of Mg-Ca intermediate alloy and Mg-Mn intermediate alloy, and the specific steps are as follows:
s1, preparing materials: polishing and cleaning pure magnesium, pure zinc, pure tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy respectively;
s2, melting: vacuum pumping the hearth, heating to 250 ℃, and heating to N 2 Purging, namely preheating the raw materials of each component in the step S1, heating to 750 ℃, preserving heat to enable the raw materials to be completely melted to form a molten mixture, and stopping heating;
s3, casting and forming: standing the molten mixture in the step S2 for a period of time to control a casting temperature, wherein the casting temperature is 700 ℃; pouring the molten mixture into a preheated graphite mould, solidifying and demoulding to obtain a magnesium alloy cast ingot;
s4, heat treatment: heating the magnesium alloy cast ingot obtained in the step S3 to 350 ℃, preserving heat for 12 hours, further heating to 500 ℃, and preserving heat for 12 hours to obtain a cast rod;
s5, turning: turning the cast rod subjected to heat treatment in the step S4, and removing oxide scales to obtain an extrusion blank;
s6, extruding: preheating the extruded blank after turning the skin in the step S5 for 30 minutes at 300 ℃, and performing hot extrusion processing at the same temperature, wherein the extrusion rate is 0.35mm/S, and the extrusion ratio is 25:1, obtaining the high-strength high-toughness corrosion-resistant Mg-1.0Zn-0.3Sn-0.3Ca-0.5Mn magnesium alloy.
The mechanical properties and weightlessness degradation test results of the high-strength and toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy obtained in the embodiment are as follows: tensile strength R m =330 MPa, yield strength R p0.2 325 MPa, elongation a=14.5%, degradation rate C R =0.24 mm/y, the test results are the average of three parallel results.
Example 5
The high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy is prepared from magnesium alloy cast ingots, and the magnesium alloy cast ingots comprise the following components in percentage by mass: zn:1.0%, sn:0.1%, ca:0.1% of Mg and unavoidable impurities in balance; wherein the atomic ratio of Sn to Ca is 1:3.
the preparation method of the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca-Mn magnesium alloy comprises the procedures of melting, casting forming, homogenizing heat treatment, extrusion and the like, wherein Mg element, zn element and Sn element are respectively added in the form of pure magnesium, pure zinc and pure tin, and Ca is added in the form of an Mg-Ca intermediate alloy, and the specific steps are as follows:
s1, preparing materials: polishing and cleaning pure magnesium, pure zinc, pure tin and Mg-Ca intermediate alloy respectively;
s2, melting: vacuum pumping the hearth, heating to 230 ℃, and heating to N 2 Purging, preheating the raw materials of each component in the step S1, heating to 720 ℃, preserving heat to enable the raw materials to be completely melted to form a molten mixture, and stopping heating;
s3, casting and forming: standing the molten mixture in the step S2 for a period of time to control a casting temperature, wherein the casting temperature is 720 ℃; pouring the molten mixture into a preheated graphite mould, solidifying and demoulding to obtain a magnesium alloy cast ingot;
s4, heat treatment: heating the magnesium alloy cast ingot obtained in the step S3 to 350 ℃, preserving heat for 12 hours, further heating to 500 ℃, and preserving heat for 12 hours to obtain a cast rod;
s5, turning: turning the cast rod subjected to heat treatment in the step S4, and removing oxide scales to obtain an extrusion blank;
s6, extruding: preheating the extruded blank after turning the skin in the step S5 for 15 minutes at 300 ℃, and performing hot extrusion processing at the same temperature, wherein the extrusion rate is 0.15 mm/S, and the extrusion ratio is 16:1, obtaining the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca magnesium alloy.
The mechanical properties and weight loss degradation test results of the high-strength and high-toughness corrosion-resistant Mg-Zn-Sn-Ca magnesium alloy obtained in the embodiment are as follows: tensile strength R m =374 MPa, yield strength R p0.2 368 MPa, elongation a=10.1% and degradation rate C R =0.21 mm/y, the test results are the average of three parallel results.
Fig. 2 is an SEM image after extrusion in step S6 of example 5. The microstructure of the magnesium alloy prepared in example 5 consists essentially of alpha-Mg, mg 2 Ca and CaMgSn phase. It can be seen that the grain structure of the extruded rod is mainly composed of ultrafine recrystallized grains and grains, the recrystallized grains are significantly refined in size, and the average recrystallized grains are 0.74 μm in size.
Comparative example 1
The hot extrusion temperature of the extrusion process in step S6 in this comparative example is 370 ℃, the other parameters and the preparation steps are the same as those of example 1, and the mechanical properties and the weight loss degradation test results of the prepared Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength R m =246 MPa, yield strength R p0.2 Extension a=27.3% at degradation rate C, =208 MPa R =0.23mm/y。
In this comparative example, compared with example 1, the rheological stress is lowered due to the excessively high extrusion temperature, so that the driving force for recrystallization is lowered, and meanwhile, the driving force for secondary growth of crystal grains is enhanced due to the rise of temperature, and under the combined action, the crystal grain size of the magnesium alloy is increased and coarsened, so that the strength is lowered.
Comparative example 2
The extrusion speed of the extrusion process in the step S6 in the comparative example is 1mm/S, the other parameters and the preparation steps are the same as those of the example 1, and the mechanical properties and the weight loss degradation test results of the prepared Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength rm=268 MPa, yield strength R p0.2 192MPa, elongation a=26.3% and degradation rate C R =0.24mm/y。
In this comparative example, compared with example 1, since the extrusion speed was too high, the friction force was increased to raise the extrusion temperature, coarsening the magnesium alloy grains, and the strength was lowered.
Comparative example 3
The magnesium alloy cast ingot provided in the comparative example comprises the following components in percentage by mass: zn:1.5%, sn:1%, ca:1.0%, mn:0.5% (i.e., the sum of the alloying element contents used is 4.0%), the balance being Mg and unavoidable impurities; the other parameters and the preparation steps are the same as those of the example 1, and the mechanical properties and the weight loss degradation test results of the Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength R m =296 MPa, yield strength R p0.2 245MPa, elongation a=14%, degradation rate C R =1.56mm/y。
Compared with the embodiment 1, the total amount of the added alloying elements reaches 4%, so that the degradation rate of the magnesium alloy is accelerated, and the corrosion resistance of the magnesium alloy is reduced, thereby reducing the strength.
Comparative example 4
The magnesium alloy ingots provided in this comparative example were all the same as example 1 in terms of the percentages of Zn, mn and Ca, except that the atomic ratio of Sn and Ca was 2:1, the content of Mg is adaptively adjusted according to the content adjustment of Sn, other parameters and preparation steps are the same as those of the embodiment 1, and the mechanical properties and weightlessness degradation test results of the prepared Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength R m =326 MPa, yield strength R p0.2 341MPa, elongation a=6.5%, degradation rate C R =0.28mm/y。
On the premise of a fixed addition amount of calcium, the increase of alloying elements increases the atomic ratio of Sn and Ca, further causes the CaMgSn phase to coarsen rapidly and can not be dissolved back by heat treatment, and the CaMgSn phase is a second phase with high melting point and is coarse in size, so that the occurrence of galvanic corrosion is aggravated, so that the atomic ratio of Sn and Ca is increased compared with the comparative example 1, the CaMgSn phase coarsens, the alloy plasticity is worsened, the galvanic corrosion is aggravated, and the synchronous deterioration of plasticity and corrosion resistance is caused.
Comparative example 5
The soaking heat treatment in the step S4 in the comparative example is a single-stage heat treatment process, the heat treatment temperature is directly increased to 500 ℃, the treatment is carried out for 24 hours, the other parameters and the preparation steps are the same as those in the example 1, and the mechanical properties and the weight loss degradation test results of the Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength R m =255 MPa, yield strength R p0.2 225MPa, elongation a=20%, degradation rate C R =0.23mm/y。
Compared with the embodiment 1, the comparative example has the advantages that the initial grains are coarse due to longer high-temperature heat treatment, so that the grain refining effect of the extrusion process is weakened, the strength is reduced and the plasticity is improved.
Comparative example 6
The magnesium alloy is prepared by adopting a magnesium alloy cast ingot, and the magnesium alloy cast ingot comprises the following components in percentage by mass: zn:2.5%, sn:0.5%, ca:0.8%, the balance being Mg and unavoidableImpurities; the other parameters and the preparation steps are the same as those of the example 1, and the mechanical properties and the weight loss degradation test results of the Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength R m =312 MPa, yield strength R p0.2 265MPa, elongation a=11%, degradation rate C R =2.13mm/y。
The main difference between the comparative example and the example 1 is that the content of Zn is beyond the limit of the invention, the synergistic effect among the elements is affected, the potential difference optimizing effect between the alpha-Mg matrix and the second phase is reduced, and the corrosion resistance of the magnesium alloy is further affected, so that the strength is reduced.
Comparative example 7
The extrusion ratio of the extrusion process in the step S6 in the comparative example is 10:1, the other parameters and the preparation steps are the same as those of the embodiment 1, and the mechanical properties and the weight loss degradation test results of the prepared Mg-Zn-Sn-Ca-Mn magnesium alloy are as follows: tensile strength R m =231 MPa, yield strength R p0.2 263MPa, elongation a=19% and degradation rate C R =0.21mm/y。
In summary, according to the high-strength and high-toughness corrosion-resistant magnesium alloy and the preparation method thereof provided by the invention, the alloy phase is optimized by designing and regulating the addition amount of alloy elements through a specific alloy system, and the performance of the existing magnesium alloy is improved by matching with a hot working process and other modes, as shown in fig. 3, the high-strength and high-toughness corrosion-resistant magnesium alloy prepared in examples 1-5 all meets the requirements of 216-368 MPa in yield strength, 282-374 MPa in tensile strength and 9-22% in elongation.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The high-strength and high-toughness corrosion-resistant magnesium alloy is characterized by comprising the following components in percentage by mass: zn:0.8-2.0%, sn:0.1-1.0%, ca:0.1-1.0%, mn:0-0.5%, and the balance Mg and unavoidable impurities, wherein the total content of Zn, sn, ca and Mn in the magnesium alloy is lower than 4%.
2. The high-strength and high-toughness corrosion-resistant magnesium alloy according to claim 1, wherein the total content of Zn, sn, ca and Mn in the magnesium alloy is not more than 3% by mass;
or the content of Zn in the magnesium alloy is 0.1-1.2%; the content of Sn is 0.1-0.4%; the content of Ca is 0.1-0.4%; mn content is 0-0.5%.
3. The high-strength and high-toughness corrosion-resistant magnesium alloy according to claim 1, wherein in the magnesium alloy, an atomic ratio of Sn element to Ca element is 1: (1-6).
4. The high strength and toughness corrosion resistant magnesium alloy according to claim 1, wherein the microstructure of said magnesium alloy comprises α -Mg, caMgSn, mg 2 At least two of Ca and beta-Mn.
5. The high strength and toughness corrosion resistant magnesium alloy according to claim 1, wherein said magnesium alloy has a yield strength of 216 MPa-368 MPa, a tensile strength of 282 MPa-374 MPa, an elongation of 9% -22%, and a weight loss degradation rate of 0.20-0.25 mm/y.
6. A method for preparing the high-strength and high-toughness corrosion-resistant magnesium alloy according to any one of claims 1 to 5, comprising the following steps:
s1, preparing materials: polishing and cleaning the raw materials of the high-strength and high-toughness corrosion-resistant magnesium alloy respectively;
s2, melting: melting the cleaned raw materials to obtain a molten mixture;
s3, casting and forming: standing the molten mixture, pouring the mixture into a preheated mold, solidifying and demolding to obtain a magnesium alloy cast ingot;
s4, heat treatment: homogenizing heat treatment is carried out on the magnesium alloy cast ingot, and then cooling is carried out to room temperature;
s5, turning: turning the ingot blank after heat treatment to remove oxide skin and obtain an extrusion blank;
s6, extruding: and preheating the extrusion blank subjected to turning and peeling, and performing hot extrusion processing to obtain the high-strength and high-toughness corrosion-resistant magnesium alloy.
7. The method for producing a high-strength and high-toughness corrosion-resistant magnesium alloy according to claim 6, wherein in step S1, the raw materials of the high-strength and high-toughness corrosion-resistant magnesium alloy include magnesium, zinc, tin, mg-Ca intermediate alloy and Mg-Mn intermediate alloy.
8. The method for producing a high strength and toughness corrosion resistant magnesium alloy according to claim 6, wherein in step S3, the casting temperature is 680 to 720 ℃;
and/or, the preheated die is a graphite die;
and/or the temperature of the preheated die is 200-300 ℃.
9. The method for preparing high strength and toughness corrosion resistant magnesium alloy according to claim 6, wherein in step S4, the homogenizing heat treatment is a two-stage heat treatment process, comprising:
the temperature of the first-stage soaking heat treatment is 300-350 ℃;
the temperature of the second-stage soaking heat treatment is 480-520 ℃;
and/or the time of the heat treatment of the first stage and the second stage is 8h-12h.
10. The method for preparing high-strength and high-toughness corrosion-resistant magnesium alloy according to claim 6, wherein in step S6, the hot extrusion process conditions are as follows:
the hot extrusion temperature is 260-350 ℃, the extrusion speed is 0.1-0.5 mm/s, and the extrusion ratio is 12:1-25:1, a step of;
and/or, the conditions of the preheating treatment include:
the preheating temperature is 260-350 ℃ and the preheating time is 15-30 min.
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