CN115491558A - Die-casting magnesium alloy and preparation method and application thereof - Google Patents
Die-casting magnesium alloy and preparation method and application thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 132
- 238000004512 die casting Methods 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- 229910052718 tin Inorganic materials 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 68
- 239000011572 manganese Substances 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 23
- 239000011575 calcium Substances 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 238000003723 Smelting Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- 150000002910 rare earth metals Chemical class 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 3
- 229910018503 SF6 Inorganic materials 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 3
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000010309 melting process Methods 0.000 claims 1
- 239000000956 alloy Substances 0.000 description 32
- 229910045601 alloy Inorganic materials 0.000 description 31
- 239000002994 raw material Substances 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000017525 heat dissipation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 3
- 229910000882 Ca alloy Inorganic materials 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 229910000914 Mn alloy Inorganic materials 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- 229910001093 Zr alloy Inorganic materials 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 229910019743 Mg2Sn Inorganic materials 0.000 description 1
- 229910017706 MgZn Inorganic materials 0.000 description 1
- 229910018657 Mn—Al Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—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
Abstract
In order to solve the problem that the existing die-casting magnesium alloy is difficult to consider both the thermal conductivity and the mechanical property, the invention provides a die-casting magnesium alloy which comprises the following components in percentage by mass: 12.5 to 18.5 percent of Zn, 0.6 to 3.5 percent of Cu, 0.001 to 0.5 percent of Sn, 0.55 to 2.5 percent of Mn and/or Zr, 0.2 to 1.8 percent of Al, 0.001 to 0.09 percent of Ca, 0.001 to 0.5 percent of Si, 0.001 to 1.8 percent of RE, 0.001 to 0.15 percent of Ag, 73.06 to 86.145 percent of Mg and less than 0.2 percent of other elements. Meanwhile, the invention also discloses a preparation method and application of the die-casting magnesium alloy. The die-casting magnesium alloy provided by the invention has high ductility required by die-casting molding, higher yield strength and tensile strength, can effectively ensure the overall strength of a product, and has excellent thermal conductivity.
Description
Technical Field
The invention belongs to the technical field of magnesium-containing alloys, and particularly relates to a die-casting magnesium alloy and a preparation method and application thereof.
Background
Die casting is one of basic forming methods of magnesium alloy, and can be used for product design of complex structural parts. The commonly used magnesium alloy die-casting material is AZ91D, the material has good flow forming performance, a large forming process window and high cost performance, and the magnesium alloy die-casting material is widely used for magnesium alloy die-casting products.
The main component elements of the AZ91D material are 8.5-9.5 wt% of aluminum, 0.45-0.9 wt% of zinc, 0.17-0.4 wt% of manganese, less than or equal to 0.05 wt% of silicon, less than or equal to 0.025 wt% of copper, less than or equal to 0.001 wt% of nickel and less than or equal to 0.004 wt% of iron. The AZ91D material is characterized by high specific strength, corrosion resistance greatly improved compared with pure magnesium, and is mainly used for shells of electrical products, small-size thin or special-shaped supports and the like, but the AZ91D material has poor heat conductivity which is only 57W/(m.k), and the heat conductivity of products with high heat conductivity requirements, such as mobile phone computer middle plates, automobile engine heat dissipation parts, automobile lamp heat dissipation structural parts and the like, cannot meet the product requirements.
Meanwhile, the material performance of the magnesium alloy is influenced by the composition of each element, and in some magnesium alloy materials, the requirement for improving the heat conductivity is met through the matching of multiple elements, and the mechanical properties such as yield strength, tensile strength and the like are reduced, so that the requirement of a structural part cannot be met, or the elongation of the magnesium alloy is reduced, so that the requirement of the magnesium alloy as a die-casting material cannot be met, fine cracks appear after die-casting forming, and the strength and the attractiveness of the material are influenced.
Disclosure of Invention
The invention provides a die-casting magnesium alloy and a preparation method and application thereof, aiming at the problem that the existing die-casting magnesium alloy is difficult to take account of both thermal conductivity and mechanical property.
The technical scheme adopted by the invention for solving the technical problems is as follows:
on one hand, the invention provides a die-casting magnesium alloy which comprises the following components in percentage by mass:
12.5 to 18.5 percent of Zn, 0.6 to 3.5 percent of Cu, 0.001 to 0.5 percent of Sn, 0.55 to 2.5 percent of Mn and/or Zr, 0.2 to 1.8 percent of Al, 0.001 to 0.09 percent of Ca, 0.001 to 0.5 percent of Si, 0.001 to 1.8 percent of RE, 0.001 to 0.15 percent of Ag, 73.06 to 86.145 percent of Mg and less than 0.2 percent of the total amount of other elements.
Optionally, the die-cast magnesium alloy comprises the following components in percentage by mass:
14 to 16.5 percent of Zn, 1.5 to 2.5 percent of Cu, 0.008 to 0.2 percent of Sn, 0.8 to 1.8 percent of Mn and/or Zr, 0.5 to 1.5 percent of Al, 0.008 to 0.04 percent of Ca, 0.01 to 0.3 percent of Si, 0.008 to 1.2 percent of RE, 0.002 to 0.1 percent of Ag, 77.36 to 83.964 percent of Mg, and the total amount of other elements is less than 0.15 percent.
Alternatively, only one of Mn and Zr is present in the die-cast magnesium alloy.
Optionally, the RE is selected from La and/or Ce.
Optionally, the other elements include one or more of Fe, co and Ni.
Optionally, the Fe content is < 0.01%.
Optionally, the Co content is less than 0.01%.
Optionally, the Ni content is less than 0.01%.
Optionally, the die-cast magnesium alloy satisfies the following conditions: the yield strength is more than 150MPa, the tensile strength is more than 222MPa, the elongation is more than or equal to 3.5 percent, and the thermal conductivity is more than or equal to 90W/(mk).
In another aspect, the present invention provides a method for preparing a die-cast magnesium alloy as described above, comprising the following steps:
weighing magnesium-containing materials, aluminum-containing materials, zinc-containing materials, manganese-containing materials and/or zirconium-containing materials, rare earth-containing materials, calcium-containing materials, copper-containing materials, silicon-containing materials, tin-containing materials and silver-containing materials according to the required proportion by element proportion in the die-casting magnesium alloy, smelting, casting to obtain magnesium alloy ingots, and then melting and die-casting the magnesium alloy ingots to form the magnesium alloy ingots.
Optionally, the melting temperature is 700-750 ℃, the casting temperature is 710-720 ℃, and the soup feeding temperature for die casting is 650-670 ℃.
Optionally, in the smelting process, under a protective atmosphere, a covering agent is added into the melt for protection, wherein the covering agent comprises MgCl 2 KCl, naCl and CaF 2 Including one or more of nitrogen, sulfur hexafluoride, and an inert gas.
Optionally, during smelting, inert gas is introduced into the melt.
Optionally, after die-casting, the die-cast magnesium alloy is subjected to artificial aging treatment at 180-280 ℃ for 0.5-7 d.
In another aspect, the present invention provides the use of the die-cast magnesium alloy as described above in electronic product structural parts and automotive structural parts.
According to the die-casting magnesium alloy, the purposes of ensuring the improvement of the heat conductivity and considering mechanical properties such as excellent yield strength, tensile strength and elongation percentage are mainly achieved, a large amount of different element additions and the addition amounts of all elements are screened, so that the composition of the die-casting magnesium alloy provided by the invention is obtained, and based on the proportion control of all elements in the composition, the die-casting magnesium alloy with excellent comprehensive performance can be obtained, is suitable for being used as a die-casting forming structural material, can effectively ensure the overall strength of a product, and is particularly suitable for being applied to electronic product shells or heat dissipation structural members in the automobile field with high requirements on heat dissipation effects based on the characteristic of excellent heat conductivity, so that the heat dissipation performance of electronic products or automobile structures can be effectively improved, and the heat accumulation is avoided.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The embodiment of the invention provides a die-casting magnesium alloy which comprises the following components in percentage by mass:
12.5 to 18.5 percent of Zn, 0.6 to 3.5 percent of Cu, 0.001 to 0.5 percent of Sn, 0.55 to 2.5 percent of Mn and/or Zr, 0.2 to 1.8 percent of Al, 0.001 to 0.09 percent of Ca, 0.001 to 0.5 percent of Si, 0.001 to 1.8 percent of RE, 0.001 to 0.15 percent of Ag, 73.06 to 86.145 percent of Mg and less than 0.2 percent of other elements.
In the description of the present invention, "Mn and/or Zr content of 0.55% to 2.5%" means: when the die-casting magnesium alloy contains one of Mn or Zr, the content of Mn or Zr is 0.55% -2.5%; when the die-cast magnesium alloy contains both Mn and Zr in an amount of 0.55% to 2.5%, other relevant descriptions may be understood in accordance with this definition.
The die-casting magnesium alloy provided by the invention has excellent thermal conductivity and mechanical property, and is suitable for application in the electronic field or the automobile field. For example, the die-cast magnesium alloy may be applied to electronic product structural members, automobile engine radiator members, or automobile lamp radiator structural members. Preferably, the die-cast magnesium alloy provided by the invention is applied to a mobile phone middle plate or a computer middle plate.
In a preferred embodiment, the die-cast magnesium alloy comprises the following components in percentage by mass:
14 to 16.5 percent of Zn, 1.5 to 2.5 percent of Cu, 0.008 to 0.2 percent of Sn, 0.8 to 1.8 percent of Mn and/or Zr, 0.5 to 1.5 percent of Al, 0.008 to 0.04 percent of Ca, 0.01 to 0.3 percent of Si, 0.008 to 1.2 percent of RE, 0.002 to 0.1 percent of Ag, 77.36 to 83.964 percent of Mg, and the total amount of other elements is less than 0.15 percent.
In some specific embodiments, the Zn content is 12.5%, 13.1%, 14.2%, 14.6%, 15.3%, 15.9%, 16.5, 17.6%, 18.1%, or 18.5%; the Cu content is 0.6%, 0.62%, 0.65%, 0.69%, 0.72%, 0.76%, 0.79%, 0.8%, 0.83%, 0.88%, 0.9%, 1.18%, 1.75%, 2.17%, 2.36%, 2.86%, 3.15%, or 3.5%; the content of Sn is 0.001%, 0.005%, 0.01%, 0.02%, 0.05%, 0.09%, 0.1%, 0.15%, 0.2%, 0.24%, 0.3%, 0.36%, 0.4%, 0.45%, or 0.5%; the content of Mn and/or Zr is 0.55%, 0.6%, 0.65%, 0.72%, 0.79%, 0.8%, 0.89%, 1%, 1.1%, 1.3%, 1.5%, 1.9%, 2.0%, 2.2%, 2.4% or 2.5%; the content of Al is 0.2%, 0.24%, 0.3%, 0.36%, 0.4%, 0.5%, 0.55%, 0.6%, 0.65%, 0.72%, 0.79%, 0.8%, 0.89%, 1%, 1.1%, 1.3%, 1.5%, or 1.8%; the content of Ca is 0.001%, 0.005%, 0.01%, 0.02%, 0.05%, 0.07% or 0.09%; the content of Si is 0.001%, 0.005%, 0.01%, 0.02%, 0.05%, 0.09%, 0.1%, 0.15%, 0.2%, 0.24%, 0.3%, 0.36%, 0.4%, 0.45% or 0.5%; the content of RE is 0.001%, 0.005%, 0.01%, 0.05%, 0.09%, 0.15%, 0.2%, 0.24%, 0.3%, 0.4%, 0.5%, 0.7%, 0.9%, 1%, 1.2%, 1.4%, 1.6%, or 1.8%; the content of Ag is 0.001%, 0.005%, 0.01%, 0.02%, 0.05%, 0.09%, 0.1% or 0.15%; the Mg content is 73.06%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85% or 86.145%.
It should be noted that, in the elements related to the present invention, the corresponding content is obtained through specific experimental tests and principle analysis, and when the content of each element is in the above range, a die-casting magnesium alloy with excellent comprehensive performance can be obtained, which has high elongation rate required for die-casting molding, and also has high yield strength and tensile strength, and can effectively ensure the overall strength of the product, and meanwhile, the die-casting magnesium alloy has excellent thermal conductivity, and when the die-casting magnesium alloy is applied to electronic products or automobile heat dissipation structural members, the heat dissipation performance of the electronic products and automobile parts can be effectively improved.
Specifically, each element and its action are analyzed as follows:
zn: the die-casting magnesium alloy has excellent fluidity and hot cracking resistance and better die-casting formability by adopting the Zn within the content range, and the Zn can act with other elements added in a magnesium matrix to form MgAlZn phase and MgZn 2 Phase and MgZnCu phase, thereby improving the mechanical property of the die-casting magnesium alloy. If the Zn content in the die-cast magnesium alloy of the present invention is too low, the fluidity of the alloy is poor,The mechanical property is reduced, and the heat cracks are increased; if the Zn content is too high, the alloy is significantly embrittled, and the elongation is significantly reduced, which is not favorable for use as a structural member.
Cu: cu can form MgZnCu phase with Mg and Zn, improve the hot cracking tendency of the alloy and promote the mechanical property and the heat-conducting property. However, the amount of Cu added cannot be too high, and too high Cu content greatly reduces the corrosion resistance of the alloy and makes the alloy brittle, which is not favorable as a die casting material.
Sn, ca: sn and Ca can synergistically play roles of solid solution strengthening, second phase strengthening and fine grain strengthening. In addition, sn and Ca form finely dispersed short rod-shaped CaMgSn ternary phases and spherical Mg with Mg 2 The strengthening effect of the Sn phase and the second phase is strengthened, and the Mg-Zn second phase is modified, so that the continuity of the aggregation Mg-Zn phase is broken, and the toughness of the alloy is improved. However, the performance improvement of the die-cast magnesium alloy is caused by the constant content of Sn and Ca, and the performance of the die-cast magnesium alloy is reduced when the content of Sn and Ca is changed, for example: if the Sn content is too high, the Mg2Sn phase becomes coarse, and the mechanical properties of the alloy are impaired.
Mn, zr: mn and Zr play similar roles in the die-casting magnesium alloy, can enhance the corrosion resistance of the die-casting magnesium alloy, refine crystal grains and improve alloy hot cracking in the addition range, wherein Mn can form a short rod-shaped Mn-Al compound reinforced alloy with Al. If the content of Mn and/or Zr in the die-casting magnesium alloy is too low, the mechanical property and the die-casting property of the die-casting magnesium alloy can be reduced; if the Mn and/or Zr content is too high, the heat conductivity and toughness of the die-cast magnesium alloy may be lowered.
In the preferred embodiment, only one of Mn and Zr is present in the die-cast magnesium alloy, because Mn and Zr are easily combined to form a poorly soluble phase and exert their element effects.
Al: al plays a role in solid solution strengthening, can form a strengthening phase with Mn \ rare earth, and in addition, al reduces the melting point of the alloy, improves the fluidity of the alloy and reduces die-casting sticking. If the Al content is too high, the thermal conductivity of the die-cast magnesium alloy is lowered.
Si: adding additives into die-casting magnesium alloyThe Si can improve the fluidity of the alloy and is beneficial to die-casting operation; on the other hand, can form Mg with Mg 2 The Si phase strengthens the alloy and improves the strength of the alloy.
RE: in the description of the invention, RE refers to rare earth metal elements, RE in the content range can refine crystal grains, form a fine and dispersed magnesium-rare earth phase, enhance the mechanical property of the die-casting magnesium alloy and improve the hot cracking of the alloy; in addition, rare earth such as La, ce and the like can reduce the solid solubility of Al in a magnesium matrix, and is beneficial to improving the heat-conducting property of the alloy.
Ag: has the effects of solid solution strengthening, strengthening alloy precipitation strengthening effect and improving the thermal conductivity of the alloy.
It should be noted that, the above is only a simplified analysis of the action of each element, and it is undeniable that, in the die-cast magnesium alloy, each element has a related action, and an increase or a decrease of any element may cause a change in the action effect of other elements, thereby causing a change in the overall performance of the die-cast magnesium alloy.
In some embodiments, the RE is selected from La and/or Ce.
In the description of the present invention, "other elements" refer to other elements than the elements in the die-cast magnesium alloy composition provided by the present invention, and may be metallic elements or non-metallic elements, and in general, "other elements" are present as impurities, generally derived from impurities contained in raw materials used in the preparation of the die-cast magnesium alloy, and the die-cast magnesium alloy provided by the present invention allows higher mechanical properties and thermal conductivity to be maintained in the presence of a certain amount of other elements, for example, the total amount of other elements is less than 0.2%, and preferably, the total amount of other elements is less than 0.15%. The excessive other elements easily cause the problems of the die-casting magnesium alloy such as reduction of elongation percentage, cracking of products, poor corrosion resistance and the like.
In some embodiments, the other elements include one or more of Fe, co, and Ni.
In tests, the inventor finds that in the die-casting magnesium alloy provided by the invention, the performance of Fe, co and Ni on the die-casting magnesium alloy is remarkably deteriorated, and therefore, the impurity content of the die-casting magnesium alloy needs to be further controlled to ensure that the die-casting magnesium alloy has better performance.
In a preferred embodiment, the Fe content is < 0.01%, more preferably, the Fe content is < 0.005%.
In a preferred embodiment, the Co content is < 0.01%, more preferably, the Co content is < 0.005%.
In a preferred embodiment, the Ni content is < 0.01%, more preferably, the Ni content is < 0.005%.
In some embodiments, the die-cast magnesium alloy is formed by die-casting and is subjected to artificial aging treatment, the treatment temperature is 180-280 ℃, and the treatment time is 0.5-7 d.
The internal stress in the die-cast magnesium alloy can be eliminated through artificial aging treatment, and the mechanical property and the thermal conductivity of the die-cast magnesium alloy are improved.
In some embodiments, the die-cast magnesium alloy satisfies the following condition: the yield strength is more than 150MPa, the tensile strength is more than 222MPa, the elongation is more than or equal to 3.5 percent, and the thermal conductivity is more than or equal to 90W/(mk).
In a preferred embodiment, the die-cast magnesium alloy satisfies the following conditions: the yield strength is 170-210MPa, the tensile strength is 240-285MPa, the elongation is 3.5-6.0%, and the thermal conductivity is 95-115W/(m.k).
The above ranges of the performance parameters of the die-cast magnesium alloy are measured after the die-cast magnesium alloy is subjected to the artificial aging treatment.
Another embodiment of the present invention provides a method for preparing a die-cast magnesium alloy as described above, comprising the following steps of:
weighing magnesium-containing material, aluminum-containing material, zinc-containing material, manganese-containing material and/or zirconium-containing material, rare earth-containing material, calcium-containing material, copper-containing material, silicon-containing material, tin-containing material and silver-containing material according to the required proportion parts in the die-casting magnesium alloy, smelting, casting to obtain magnesium alloy ingots, and then melting and die-casting the magnesium alloy ingots to form the magnesium alloy ingots.
The magnesium-containing material, the aluminum-containing material, the zinc-containing material, the manganese-containing material or the zirconium-containing material, the rare earth-containing material, the calcium-containing material, the copper-containing material, the silicon-containing material, the tin-containing material and the silver-containing material can be materials capable of providing various elements required for preparing the die-casting magnesium alloy of the invention, and can be alloys or pure metals containing the elements as long as the components in the die-casting magnesium alloy obtained by smelting the added magnesium alloy raw material are within the ranges. Preferably, the raw material of the die-cast magnesium alloy may include pure Mg or Mg alloy, pure Al or Al alloy, pure Zn or Zn alloy, pure Mn or Mn alloy, pure Zr or Zr alloy, pure rare earth or rare earth alloy, pure Ca or Ca alloy, pure Cu or Cu alloy, pure Si or Si alloy, pure Sn or Sn alloy, pure Ag or Ag alloy. More preferably, the raw materials of the die-cast magnesium alloy include pure Mg, pure Al, pure Zn, mg-Mn alloy, mg-Zr alloy, mg-rare earth alloy, mg-Ca alloy, mg-Cu alloy, mg-Si alloy, pure Sn, mg-Ag alloy.
In some embodiments, the melting temperature is 700 ℃ to 750 ℃, the casting temperature is 710 ℃ to 720 ℃, and the feeding temperature for die casting is 650 ℃ to 670 ℃.
In a preferred embodiment, the temperature for smelting the magnesium-containing material is 720-740 ℃, and the smelting temperature after adding the aluminum-containing material, the zinc-containing material, the manganese-containing material or the zirconium-containing material, the rare earth-containing material, the calcium-containing material, the copper-containing material, the silicon-containing material, the tin-containing material and the silver-containing material is 740-750 ℃.
In some embodiments, during the melting, the covering agent is added into the melt for protection under a protective atmosphere, and the covering agent comprises MgCl 2 KCl, naCl and CaF 2 Including one or more of nitrogen, sulfur hexafluoride and inert gases.
Magnesium is active chemically at high temperature, and can avoid the contact oxidation of magnesium alloy with air in the smelting process under the action of protective atmosphere and covering agent.
In some embodiments, inert gas is introduced into the melt during smelting.
The pressure and time of introducing argon are controlled to make the magnesium alloy melt be boiled and refined, so as to achieve the purposes of homogenizing chemical components and temperature, accelerating chemical reaction, removing harmful gas and impurities and purifying the melt.
In some embodiments, after die-casting, the die-casting magnesium alloy is subjected to artificial aging treatment at the temperature of 180-280 ℃ for 0.5-7 d.
The internal stress in the die-cast magnesium alloy can be eliminated through artificial aging treatment, and the mechanical property and the thermal conductivity of the die-cast magnesium alloy are improved.
In some embodiments, after the artificial aging treatment is completed, the die-cast magnesium alloy is left to cool naturally at room temperature.
Another embodiment of the present invention provides the use of the die-cast magnesium alloy as described above in electronic product structural parts and automotive structural parts.
The present invention is further illustrated by the following examples.
TABLE 1
Example 1
This embodiment is used to illustrate the die-cast magnesium alloy and the preparation method thereof disclosed by the present invention, and the method includes the following steps:
according to the composition of the die-casting magnesium alloy shown in the example 1 in the table 1, simple substances containing various elements and alloy raw materials are prepared;
adding pure Mg into a smelting furnace, and smelting at 720-740 ℃; after pure Mg is melted, adding pure Al, pure Zn, mg-Mn alloy, mg-Zr alloy, mg-rare earth alloy and Mg-Ca alloy, mg-Cu alloy, mg-Si alloy, pure Sn, mg-Ag alloy, and MgCl accounting for 3 wt% of the total amount of the alloy raw materials 2 Smelting at 740-750 ℃, blowing 99.99% of high-purity argon gas in the smelting process, stirring and uniformly stirring to obtain alloy melt; casting the alloy solution to obtain a magnesium alloy ingot; melting and die-casting a magnesium alloy ingot, wherein the feeding temperature for die-casting is 650-670 ℃; and (3) after die-casting forming, carrying out aging treatment on the die-casting magnesium alloy at 200 ℃, wherein the duration is 1h, and naturally cooling to room temperature after the aging treatment is finished to obtain the die-casting magnesium alloy.
Examples 2 to 43
Examples 2 to 43, which are for explaining the aluminum alloy and the method for manufacturing the same disclosed in the present invention, include most of the operation steps in example 1, except that:
the elementary substances and alloy raw materials of each element were calculated from the respective element components of the die-cast magnesium alloys shown in examples 2 to 43 in table 1, and the elementary substances and alloy raw materials of each element were added to a melting furnace to be melted.
The other operation was conducted in accordance with example 1 to obtain a die-cast magnesium alloy
Comparative examples 1 to 21
Comparative examples 1 to 21 for comparative illustration of the aluminum alloy and the method for manufacturing the same disclosed in the present invention, which includes most of the operational steps of example 1, except that:
the simple substances and alloy raw materials of the elements are calculated according to the components of the elements of the die-casting magnesium alloy shown in comparative examples 1 to 21 in table 1, and the simple substances and the alloy raw materials of the elements are added into a smelting furnace for smelting.
The other operations were carried out in the same manner as in example 1 to obtain a die-cast magnesium alloy.
Performance test
The die-cast magnesium alloys prepared in the above examples 1 to 43 and comparative examples 1 to 21 were subjected to the following performance tests:
and (3) magnesium alloy tensile test: according to the test method of ISO 6892-1, the smelted magnesium alloy melt is injected into a die cavity by adopting pressure casting equipment to obtain a tensile casting with the wall thickness of 3mm, and a universal mechanical testing machine is adopted to carry out tensile test to obtain the yield strength, the tensile strength and the elongation percentage, wherein the yield strength is the yield limit generating 0.2% of residual deformation, and the elongation percentage is the elongation at break.
Die-casting formability: in the die-casting process, the forming condition of the alloy die-casting thin-wall part with the thickness of 0.5mm is observed for judgment, and whether the forming is complete or not and whether cracks exist are mainly concerned.
Test of thermal conductivity: according to the test method of ASTM E1461-07, a magnesium alloy wafer having a diameter of 12.7mm and a thickness of 3mm was subjected to a test of thermal conductivity by a laser flash method.
The results of the tests obtained are filled in table 2.
TABLE 2
As can be seen from the test results in table 2, compared with the die-casting magnesium alloy outside the element range provided by the present invention, the die-casting magnesium alloy provided by the present invention has better mechanical strength, can meet the requirements of the die-casting process, and simultaneously has better heat conductivity, elongation and die-casting formability, and particularly, the die-casting magnesium alloy provided by the present invention has excellent heat conductivity, and is particularly suitable for application in heat dissipation materials.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (15)
1. The die-casting magnesium alloy is characterized by comprising the following components in percentage by mass:
12.5 to 18.5 percent of Zn, 0.6 to 3.5 percent of Cu, 0.001 to 0.5 percent of Sn, 0.55 to 2.5 percent of Mn and/or Zr, 0.2 to 1.8 percent of Al, 0.001 to 0.09 percent of Ca, 0.001 to 0.5 percent of Si, 0.001 to 1.8 percent of RE, 0.001 to 0.15 percent of Ag, 73.06 to 86.145 percent of Mg and less than 0.2 percent of other elements.
2. The die-cast magnesium alloy according to claim 1, characterized in that the die-cast magnesium alloy comprises the following components in mass percent:
14 to 16.5 percent of Zn, 1.5 to 2.5 percent of Cu, 0.008 to 0.2 percent of Sn, 0.8 to 1.8 percent of Mn and/or Zr, 0.5 to 1.5 percent of Al, 0.008 to 0.04 percent of Ca, 0.01 to 0.3 percent of Si, 0.008 to 1.2 percent of RE, 0.002 to 0.1 percent of Ag, 77.36 to 83.964 percent of Mg, and the total amount of other elements is less than 0.15 percent.
3. The die-cast magnesium alloy according to claim 1, characterized in that only one of Mn and Zr is present in the die-cast magnesium alloy.
4. Die cast magnesium alloy according to claim 1, characterized in that the RE is selected from La and/or Ce.
5. The die-cast magnesium alloy according to claim 1, wherein the other elements include one or more of Fe, co and Ni.
6. Die-cast magnesium alloy according to claim 5, characterized in that the Fe content in the die-cast magnesium alloy is < 0.01%.
7. Die-cast magnesium alloy according to claim 5, characterized in that the Co content in the die-cast magnesium alloy is < 0.01%.
8. The die-cast magnesium alloy according to claim 5, wherein the Ni content in the die-cast magnesium alloy is < 0.01%.
9. The die-cast magnesium alloy according to claim 1, characterized in that the die-cast magnesium alloy satisfies the following condition: the yield strength is more than 150MPa, the tensile strength is more than 222MPa, the elongation is more than or equal to 3.5 percent, and the thermal conductivity is more than or equal to 90W/(m.k).
10. The method for producing die-cast magnesium alloy according to any of claims 1 to 8, characterized by comprising the following steps of:
weighing magnesium-containing materials, aluminum-containing materials, zinc-containing materials, manganese-containing materials and/or zirconium-containing materials, rare earth-containing materials, calcium-containing materials, copper-containing materials, silicon-containing materials, tin-containing materials and silver-containing materials according to the required proportion by element proportion in the die-casting magnesium alloy, smelting, casting to obtain magnesium alloy ingots, and then melting and die-casting the magnesium alloy ingots to form the magnesium alloy ingots.
11. The method for preparing die-cast magnesium alloy according to claim 10, wherein the melting temperature is 700 ℃ to 750 ℃, the casting temperature is 710 ℃ to 720 ℃, and the feeding temperature for die-casting is 650 ℃ to 670 ℃.
12. The method for preparing die-cast magnesium alloy as claimed in claim 10, wherein during the melting process, a covering agent is added into the melt for protection under a protective atmosphere, wherein the covering agent comprises MgCl 2 KCl, naCl and CaF 2 Including one or more of nitrogen, sulfur hexafluoride, and an inert gas.
13. The method for producing die-cast magnesium alloy as claimed in claim 10, wherein an inert gas is introduced into the melt during the melting.
14. The method for preparing the die-cast magnesium alloy according to claim 10, wherein the die-cast magnesium alloy is subjected to artificial aging treatment after die-cast molding, the treatment temperature is 180 ℃ to 280 ℃, and the treatment time is 0.5h to 7d.
15. Use of the die-cast magnesium alloy according to any one of claims 1 to 8 for structural members of electronic products and automotive members.
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