CN113584364B - Method for synergistically improving mechanical and corrosion properties of high-lithium-content ultralight magnesium-lithium-based alloy - Google Patents
Method for synergistically improving mechanical and corrosion properties of high-lithium-content ultralight magnesium-lithium-based alloy Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 52
- 238000005260 corrosion Methods 0.000 title claims abstract description 40
- 230000007797 corrosion Effects 0.000 title claims abstract description 40
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000001989 lithium alloy Substances 0.000 claims abstract description 19
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000005728 strengthening Methods 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 11
- 239000011780 sodium chloride Substances 0.000 claims description 9
- 230000004580 weight loss Effects 0.000 claims description 8
- 229910000905 alloy phase Inorganic materials 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 239000011701 zinc Substances 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 230000007123 defense Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005482 strain hardening Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019400 Mg—Li Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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Abstract
The method for synergistically improving the mechanical and corrosion properties of the high-lithium-content ultra-light magnesium-lithium-based alloy comprises the following steps of 8-14 wt.% of Li, wherein the total content of main alloy elements (Zn, RE, Zr and the like) is lower than 8 wt.%, the total content of inclusion elements (Fe, Cu and the like) is lower than 0.001 wt.%, and the balance is Mg. The preparation method is a method for synergistically improving the mechanical property and the corrosion property by regulating and controlling the surface exposed area fraction of a beta-Li matrix phase in the alloy and the quantity, size and distribution of dispersion strengthening precipitated particles in the matrix phase, and particularly relates to a large plastic processing and dynamic strain aging precipitation regulation and control treatment process system capable of obviously improving the strength of a magnesium-lithium based alloy and greatly reducing the corrosion rate of the magnesium-lithium based alloy. The invention obviously improves the strength and corrosion resistance of the magnesium-lithium alloy while ensuring the plasticity of the magnesium-lithium based alloy, and effectively weakens the severity of local corrosion of the alloy. The invention has the advantages of simple equipment, low cost, wide applicability, adjustable size and specification and simple operation.
Description
Technical Field
The invention relates to an effective method and a processing and preparation technology suitable for synergistically improving mechanical and corrosion properties of a high-lithium-content ultralight magnesium-lithium-based alloy, in particular to a control method for meeting the requirement of a magnesium-lithium alloy on higher comprehensive service performance under engineering application conditions.
Background
With the rapid development of national economy and scientific technology, the problems of energy conservation and emission reduction existing in the engineering application field are urgently needed to be solved, so that the equipment is lightened and becomes the subject of current economic development. Under the traction of the requirement of light weight, the method provides opportunities for the research and development and engineering application of high-performance light metal materials. In comparison, the magnesium-lithium alloy has the lowest density and higher specific strength and specific rigidity, so that the magnesium-lithium alloy has stronger application prospect in high-end manufacturing fields such as aerospace, national defense and military industry and the like. Therefore, the large-scale application of the magnesium-lithium alloy is expected to solve the problem of overall light weight of engineering equipment, can greatly improve the flexibility of equipment operation, and finally contributes to improving the overall national economy and national defense military level of China. However, the conventional magnesium-lithium alloys have problems of low absolute engineering strength and poor corrosion resistance, so that it is difficult to satisfy the performance standards of engineering members for their service performance and to find practical engineering applications. In recent years, researches show that a compact LiOH film layer is generated on the surface of a beta-Li phase in the magnesium-lithium alloy in the corrosion process, and the beta-Li phase can play a good protection role on a matrix. However, for the alpha-Mg phase in the alloy, the corrosion products Mg (OH) formed on the surface thereof2Is loose and is difficult to have the protection effect on the matrix.Although pure β -Li phase has a strong corrosion resistance, its absolute strength is low and it is difficult to use it as a structural member. Based on the above analysis, while the exposed area of the β -Li phase in the magnesium-lithium alloy can be increased, a certain number of high-efficiency dispersion-strengthened precipitated phase particles are formed in the matrix by dynamic strain aging treatment. In addition, the alloy structure can be refined by combining a plastic deformation processing technology with large deformation, and the matrix can be obviously strengthened due to work hardening. By combining the processing and treating means, the effect of synergistically improving the mechanical property and the corrosion property of the ultralight magnesium-lithium-based alloy can be realized, the bottleneck problem of limiting the insufficient performance of the traditional magnesium-lithium alloy is effectively solved, and a candidate material with high service performance is provided for solving the light weight problem in the manufacturing field of national defense military industry and high-end equipment.
Disclosure of Invention
The invention aims to provide a method for synergistically improving the mechanical and corrosion properties of a high-lithium-content ultralight magnesium-lithium-based alloy, and solves the bottleneck problem of limiting insufficient service performance of the magnesium-lithium alloy in the engineering application field.
The method for synergistically improving the mechanical and corrosion properties of the high-lithium-content ultralight magnesium-lithium-based alloy is characterized by comprising the following steps of: the magnesium-lithium alloy comprises 8-14 wt.% Li, the total content of main alloy elements (Zn: 3-6 wt.%, RE: 1-2 wt.%, Zr: 0.8-1 wt.% and the like) is less than 8 wt.%, the total content of inclusion elements (Fe, Cu and the like) is less than 0.001 wt.%, and the balance is Mg.
The alloy needs to be subjected to homogenization treatment for 2 hours at 300-500 ℃ to ensure that a large alloy phase in the alloy is solid-dissolved, and the size of a residual particle phase is less than 1 mu m.
The magnesium-lithium-based alloy is subjected to rolling deformation with the reduction rate of 10-20% per pass at room temperature until the total reduction rate of the plate is 80%, the length-width ratio of a beta-Li matrix phase after large deformation is strictly controlled to be more than 20, and the exposed area ratio is more than 60%.
The dynamic strain aging precipitation treatment is carried out for 1-5 hours at the temperature of 100-200 ℃, the applied tensile strain amount is 0.2-0.5%, and nano-scale precipitation strengthening particles with uniform distribution are formed in a matrix phase.
The weight loss rate of the sodium chloride solution in 0.1M NaCl solution at room temperature is 0.1-0.5 mg/cm2Day, corrosion current icorr1 to 5 mu A/cm2Macroscopically, the uniform corrosion is obvious, and the height difference of the corrosion surface is 10-50 mu m. Meanwhile, the yield strength of the alloy is 250-300 MPa, the tensile strength is 290-360 MPa, the elongation is 20-40%, and the density is 1.40-1.65 g/cm3。
The design idea of the invention is as follows: the method is characterized in that a high-lithium-content ultralight magnesium-lithium-based alloy material is reasonably selected, the size of a residual particle phase is controlled to be smaller than 1 mu m by adopting homogenization treatment, the length-width ratio and the exposed area ratio of a beta-Li matrix phase are controlled by adopting multi-pass accumulative rolling, the effects of tissue refinement and work hardening are achieved, and the quantity and the distribution of nanoscale precipitation strengthening particles in the matrix are regulated and controlled by adopting pre-stretching dynamic strain aging treatment. The corrosion resistance of the alloy is improved by utilizing the protective effect of forming a LiOH film layer on the surface of a beta-Li phase in the alloy. The mechanical strength of the alloy is improved by utilizing coupled strengthening modes such as structure refinement, work hardening, dispersion precipitation strengthening and the like, and the aim of synergistically improving the mechanical property and the corrosion resistance of the alloy is finally achieved.
The invention has the advantages and beneficial effects that:
1. according to the invention, the high-lithium content ultra-light magnesium-lithium-based alloy material with a strong engineering application prospect is selected, so that the mechanical property and the corrosion property of the alloy are synergistically improved, and the competitiveness of the alloy as an engineering structure material can be remarkably improved.
2. The high-lithium-content magnesium-lithium-based alloy has universality, provides reference for the development of high-service-performance industrial magnesium-lithium alloy, and expands the engineering field of possible application of the magnesium-lithium-based alloy.
3. The invention has the advantages of simple equipment, lower cost, wide applicability, adjustable size and specification and simple operation.
Drawings
FIG. 1 is a selection of a microstructure information comparison of Mg-8 wt.% Li-6 wt.% Zn-0.8 wt.% Y-0.8 wt.% Zr for a magnesium-lithium alloy after heavy reduction rolling and dynamic strain aging (example one). In FIGS. 1(a) and (b), photographs of microstructures before and after rolling are shown, respectively, in which black portions are β -Li phases and white portions are α -Mg phases. Because the beta-Li phase has strong plastic deformation capability and large area fraction, the length-width ratio can be indirectly obtained through the shape of the alpha-Mg phase.
Detailed Description
The present invention is further described with reference to the following specific embodiments and accompanying drawings, wherein the examples are provided for illustrating the present invention and not for limiting the present invention, and the scope of the present invention is not limited to the following specific examples.
Example one
I) selection of alloys
Selecting a magnesium-lithium alloy of Mg, 8 wt.% of Li, 6 wt.% of Zn, 0.8 wt.% of Y and 0.8 wt.% of Zr, wherein the magnesium-lithium alloy comprises the following chemical components in percentage by mass: 8% of Li, 6% of Zn, 0.8% of Y, 0.8% of Zr, the total content of inclusion elements (Fe, Cu and the like) is less than 0.001 wt.%, and the balance is Mg;
II), proportioning and smelting
Weighing corresponding raw materials of pure magnesium, pure lithium, pure zinc, pure yttrium and Mg-33 wt.% Zr intermediate alloy according to the weight percentage of the chemical components, wherein the total weight is 10 kg;
and (3) putting the prepared alloy raw materials into a vacuum smelting furnace, keeping the temperature for half an hour at 760 ℃, stirring in the furnace, standing for half an hour at 730 ℃, and casting in the furnace. Homogenizing the cast ingot at 450 ℃ for 2 hours to ensure that a bulk alloy phase in the alloy is solid-dissolved, and the size of a residual particle phase is less than 1 mu m;
III) deformation processing
Under the condition of room temperature, carrying out rolling deformation with the reduction rate of 10% per pass on the magnesium-lithium-based alloy until the total reduction rate of the plate is 80%, strictly controlling the length-width ratio of the beta-Li matrix phase after large deformation to be more than 20, and the exposed area ratio to be more than 60%;
IV) dynamic ageing treatment
Carrying out dynamic strain aging precipitation treatment for 3 hours at 180 ℃, wherein the applied tensile strain is 0.2%, so that uniformly distributed nano-scale precipitation strengthening particles are formed in a matrix phase;
v), mechanical and Corrosion Performance testing
And cutting a tensile and corrosive sample by utilizing linear cutting, wherein the surface of the sample is parallel to the rolling surface. Then, the strain rate at room temperature was 1X 10-3s-1The tensile properties of (2) were tested by soaking and electrochemical experiments in 0.1M NaCl solution. After the corrosion experiment is finished, removing corrosion products on the surface of the sample by using a soft brush, weighing the lost weight of the sample, and calculating the weight loss rate. And 3-dimensional morphology observation is carried out on the surface of the sample, and the flatness is measured. The properties measured by the experiment are: the rate of weight loss in a 0.1M NaCl solution at room temperature was 0.4mg/cm2Day, corrosion Current icorrIs 4 muA/cm2Macroscopically, a uniform corrosion with a difference in height of the corrosion surface of 45 μm is evident. Meanwhile, the yield strength of the alloy is 300MPa, the tensile strength is 350MPa, the elongation is 30 percent, and the density is 1.55g/cm3。
Example two
I) selection of alloys
Selecting a magnesium-lithium alloy of Mg, 10 wt.% of Li, 6 wt.% of Zn, 0.8 wt.% of Y and 0.8 wt.% of Zr, wherein the magnesium-lithium alloy comprises the following chemical components in percentage by mass: 10% of Li, 6% of Zn, 0.8% of Y, 0.8% of Zr, the total content of inclusion elements (Fe, Cu and the like) is less than 0.001 wt.%, and the balance is Mg;
II), proportioning and smelting
The ingredients of example one were referenced. And (3) putting the prepared alloy raw materials into a vacuum smelting furnace, keeping the temperature for half an hour at 760 ℃, stirring in the furnace, standing for half an hour at 730 ℃, and casting in the furnace. Homogenizing the cast ingot at 450 ℃ for 1.5 hours to ensure that a bulk alloy phase in the alloy is solid-dissolved, and the size of a residual particle phase is less than 1 mu m;
III) deformation processing
Under the condition of room temperature, carrying out rolling deformation with the reduction rate of 15% per pass on the magnesium-lithium-based alloy until the total reduction rate of the plate is 80%, strictly controlling the length-width ratio of the beta-Li matrix phase after large deformation to be more than 20, and the exposed area ratio to be more than 60%;
IV) dynamic ageing treatment
Carrying out dynamic strain aging precipitation treatment for 3 hours at 150 ℃, wherein the applied tensile strain is 0.3%, so that uniformly distributed nano-scale precipitation strengthening particles are formed in a matrix phase;
v), mechanical and Corrosion Performance testing
And cutting a tensile and corrosive sample by utilizing linear cutting, wherein the surface of the sample is parallel to the rolling surface. Then, the strain rate at room temperature was 1X 10-3s-1The tensile properties of (2) were tested by soaking and electrochemical experiments in 0.1M NaCl solution. After the corrosion experiment is finished, removing corrosion products on the surface of the sample by using a soft brush, weighing the lost weight of the sample, and calculating the weight loss rate. And 3-dimensional morphology observation is carried out on the surface of the sample, and the flatness is measured. The properties measured by the experiment are: the rate of weight loss in a 0.1M NaCl solution at room temperature was 0.2mg/cm2Day, corrosion current icorrIs 3 mu A/cm2Macroscopically, the uniform etching is obvious, and the height difference of the etching surface is 35 mu m. Meanwhile, the yield strength of the alloy is 290MPa, the tensile strength is 340MPa, the elongation is 40 percent, and the density is 1.50g/cm3。
EXAMPLE III
I) selection of alloys
Selecting Mg-12 wt.% Li-6 wt.% Zn-1.2 wt.% Y-0.8 wt.% Zr, wherein the Mg-Li alloy comprises the following chemical components in percentage by mass: 12% of Li, 6% of Zn, 1.2% of Y, 0.8% of Zr, the total content of inclusion elements (Fe, Cu and the like) is less than 0.001 wt.%, and the balance is Mg;
II), proportioning and smelting
The ingredients of example one were referenced. And (3) putting the prepared alloy raw materials into a vacuum smelting furnace, keeping the temperature for half an hour at 760 ℃, stirring in the furnace, standing for half an hour at 730 ℃, and casting in the furnace. Homogenizing the cast ingot at 480 ℃ for 2 hours to ensure that a large alloy phase in the alloy is solid-dissolved, and the size of a residual particle phase is less than 1 mu m;
III) deformation processing
Under the condition of room temperature, performing rolling deformation with the reduction rate of 20% per pass on the magnesium-lithium-based alloy until the total reduction rate of the plate is 80%, strictly controlling the length-width ratio of the beta-Li matrix phase after large deformation to be more than 20, and enabling the exposed area ratio to be more than 60%;
IV) dynamic ageing treatment
Carrying out dynamic strain aging precipitation treatment for 1 hour at the temperature of 200 ℃, wherein the applied tensile strain is 0.5 percent, so that uniformly distributed nano-scale precipitation strengthening particles are formed in a matrix phase;
v), mechanical and Corrosion Performance testing
And cutting a tensile and corrosive sample by utilizing linear cutting, wherein the surface of the sample is parallel to the rolling surface. Then, the strain rate at room temperature was 1X 10-3s-1The tensile properties of (2) were tested by soaking and electrochemical experiments in 0.1M NaCl solution. After the corrosion experiment is finished, removing corrosion products on the surface of the sample by using a soft brush, weighing the lost weight of the sample, and calculating the weight loss rate. And 3-dimensional morphology observation is carried out on the surface of the sample, and the flatness is measured. The properties measured by the experiment are: the rate of weight loss in a 0.1M NaCl solution at room temperature was 0.1mg/cm2Day, corrosion current icorrIs 1 muA/cm2Macroscopically, the uniform etching is obvious, and the height difference of the etching surface is 20 μm. Meanwhile, the yield strength of the alloy is 270MPa, the tensile strength is 310MPa, the elongation is 50 percent, and the density is 1.46g/cm3。
Claims (2)
1. The method for synergistically improving the mechanical and corrosion properties of the high-lithium-content ultralight magnesium-lithium-based alloy is characterized by comprising the following steps of: the magnesium-lithium alloy comprises 8-14 wt.% of Li, the total content of main alloy elements is less than 8 wt.%, and the main alloy elements are Zn: 3-6 wt.%, RE: 1-2 wt.%, Zr: 0.8-1 wt.%; the total content of inclusion elements is less than 0.001 wt.%, and the balance is Mg;
homogenizing the alloy for 2 hours at 300-500 ℃ to ensure that a large alloy phase in the alloy is solid-dissolved, and the size of a residual particle phase is less than 1 mu m;
under the condition of room temperature, performing rolling deformation with the reduction rate of 10-20% per pass on the magnesium-lithium-based alloy until the total reduction rate of the plate is 80%, strictly controlling the length-width ratio of the beta-Li matrix phase after large deformation to be more than 20, and enabling the exposed area ratio to be higher than 60%;
and carrying out dynamic strain aging precipitation treatment for 1-5 hours at the temperature of 100-200 ℃, wherein the applied tensile strain is 0.2-0.5%, so that uniformly distributed nano-scale precipitation strengthening particles are formed in the matrix phase.
2. The method for synergistically improving the mechanical and corrosion properties of the high-lithium-content ultralight magnesium-lithium-based alloy according to claim 1, wherein the method comprises the following steps: the weight loss rate of the catalyst in 0.1M NaCl solution at room temperature is 0.1-0.5 mg/cm2Day, corrosion current icorr1 to 5 muA/cm2Macroscopically, the uniform corrosion is obvious, and the height difference of the corrosion surface is 10-50 mu m; meanwhile, the alloy has yield strength of 250-300 MPa, tensile strength of 290-360 MPa, elongation of 20-40% and density of 1.40-1.65 g/cm3。
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