CN109554596B - Wrought magnesium alloy with high ductility and preparation method thereof - Google Patents
Wrought magnesium alloy with high ductility and preparation method thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 36
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 25
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 25
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 25
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 23
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052788 barium Inorganic materials 0.000 claims abstract description 23
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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 claims abstract description 23
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 23
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 112
- 239000000956 alloy Substances 0.000 claims description 112
- 238000003756 stirring Methods 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 69
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- 238000007670 refining Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- DJPURDPSZFLWGC-UHFFFAOYSA-N alumanylidyneborane Chemical compound [Al]#B DJPURDPSZFLWGC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010309 melting process Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- 229910018503 SF6 Inorganic materials 0.000 claims description 3
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229910001172 neodymium magnet 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 239000013078 crystal Substances 0.000 description 17
- 238000009472 formulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 potassium fluoroborate Chemical compound 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 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
- C22C23/02—Alloys based on magnesium with aluminium 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a wrought magnesium alloy with high ductility, which comprises the following raw materials in parts by weight: 83 parts of magnesium, 5 parts of aluminum, 1 part of zinc, 1 part of zirconium, 0.8 part of lanthanum, 0.8 part of yttrium, 0.8 part of gadolinium, 1.5 parts of calcium, 1 part of barium, 2 parts of manganese, 0.5 part of strontium and 0.3 part of antimony. Also discloses a preparation method of the wrought magnesium alloy with high ductility. The wrought magnesium alloy prepared by the method has small grain size, high ductility and excellent mechanical property.
Description
Technical Field
The invention relates to a wrought magnesium alloy. More specifically, the invention relates to a wrought magnesium alloy with high ductility, and belongs to the technical field of magnesium alloy preparation.
Background
The magnesium alloy has the advantages of high specific strength and specific rigidity, good heat and electric conductivity, damping and shock absorption, electromagnetic shielding, easy processing and forming, easy recovery and the like, is widely applied to the fields of automobiles, electronic communication, aerospace, national defense and military and the like, and is known as a green engineering material in the 21 st century. According to the different forming methods, the magnesium alloy is divided into two types, namely deformed magnesium alloy and cast magnesium alloy. Compared with the cast magnesium alloy, the wrought magnesium alloy can obtain higher strength, better ductility and more diversified mechanical properties by controlling the structure of the material and applying a proper heat treatment process so as to meet the application requirements of diversified engineering structural members, thereby having greater development potential. However, the existing wrought magnesium alloy still has the defects of insufficient ductility and incapability of meeting the requirements of certain special applications.
Disclosure of Invention
An object of the present invention is to provide a wrought magnesium alloy with high ductility, which has good ductility and can compensate for the limited application of the wrought magnesium alloy due to insufficient ductility.
It is still another object of the present invention to provide a method for preparing a wrought magnesium alloy having high ductility, which can prevent the burning loss of alloying elements during melting, and at the same time, can effectively refine grains and avoid the formation of intermetallic compounds, thereby significantly improving the ductility of the wrought magnesium alloy.
To achieve these objects and other advantages in accordance with the present invention, there is provided a wrought magnesium alloy with high ductility, comprising the following raw materials in parts by weight: 83 parts of magnesium, 5 parts of aluminum, 1 part of zinc, 1 part of zirconium, 0.8 part of lanthanum, 0.8 part of yttrium, 0.8 part of gadolinium, 1.5 parts of calcium, 1 part of barium, 2 parts of manganese, 0.5 part of strontium and 0.3 part of antimony.
Preferably, the magnesium is pure magnesium ingot, the aluminum is pure aluminum ingot, the zinc is pure zinc ingot, and the purity of the zirconium, the lanthanum, the yttrium, the gadolinium, the calcium, the barium, the manganese, the strontium and the antimony is more than or equal to 99%.
The object of the present invention can be further achieved by a method for preparing a wrought magnesium alloy having high ductility, the method comprising the steps of:
the method comprises the following steps: weighing magnesium and aluminum according to the weight parts, preheating at 100 ℃ for 3 hours, putting into a magnesium alloy furnace, covering the surfaces of the magnesium and the aluminum with mixed powder of graphite, calcium chloride and potassium chloride in a mass ratio of 1:2:2, introducing mixed gas of nitrogen and argon in a volume ratio of 2:1 into the magnesium alloy furnace, raising the temperature of the magnesium alloy furnace to melt the magnesium and the aluminum, stirring for 15 minutes, removing slag to obtain first alloy liquid, wherein the mixed powder of the graphite, the calcium chloride and the potassium chloride is subjected to ball milling for 5 hours at a rotating speed of 800r/min and a ball-to-material ratio of 4:1 before use, and is taken out and then passes through a 300-mesh screen;
step two: weighing zinc, zirconium, lanthanum, yttrium, gadolinium, calcium, barium, manganese, strontium and antimony according to the weight parts, respectively preheating for 3 hours at 150 ℃, then adding preheated calcium, barium, manganese, strontium and antimony into the first alloy liquid prepared in the step one, heating, stirring for 15 minutes after the calcium, barium, manganese, strontium and antimony are completely melted, then adding preheated zinc, zirconium, lanthanum, yttrium and gadolinium, heating, stirring for 20 minutes after the zinc, zirconium, lanthanum, yttrium and gadolinium are completely melted, and removing molten slag to obtain a second alloy liquid, wherein a mixed gas of nitrogen and argon with a volume ratio of 2:1 is introduced in the whole melting process;
step three: adding the preheated aluminum-silicon intermediate alloy into the second alloy liquid prepared in the step two, heating, after the aluminum-silicon intermediate alloy is completely melted, adding preheated Al-B intermediate alloy, heating until the Al-B intermediate alloy is completely molten, adding potassium fluoborate, heating to 730 ℃, placing under the conditions that the ultrasonic frequency is 30KHz and the stirring speed is 1000r/min, stirring and ultrasonic treating for 1h to obtain a third alloy liquid, wherein the adding amount of the aluminum-silicon intermediate alloy is 5 percent of the weight of the second alloy liquid, the adding amount of the aluminum-boron intermediate alloy is 0.8 percent of the weight of the second alloy liquid, the adding amount of the potassium fluoborate is 2 percent of the weight of the second alloy liquid, continuously introducing a mixed gas of nitrogen and argon with the volume ratio of 2:1 in the whole melting and stirring process, wherein the preheating processes of the aluminum-silicon intermediate alloy and the aluminum-boron intermediate alloy both comprise the following steps: preheating for 3h at 150 ℃;
step four: heating the third alloy liquid prepared in the third step to 760 ℃, then adding a magnesium alloy refining agent under stirring at a stirring speed of 500r/min, refining for 1h, standing for 20min, and finally removing sediments to obtain refined alloy liquid, wherein the addition amount of the magnesium alloy refining agent is 5% of the weight of the third alloy liquid, and a mixed gas of nitrogen and argon with a volume ratio of 2:1 is continuously introduced in the refining process;
step five: and cooling the refined alloy liquid prepared in the fourth step to 700 ℃, then casting into a cast ingot, tempering the cast ingot at 500 ℃ for 3h, cooling to 400 ℃ for extrusion to prepare a magnesium alloy sheet, preserving the heat of the magnesium alloy sheet at 150 ℃ for 20h, and then naturally cooling to prepare a high-ductility deformed magnesium alloy finished product.
Preferably, in the fifth step, the refined alloy liquid is refined after being cooled and before being cast, and the refining process comprises the following specific steps: the method comprises the steps of placing refined alloy liquid in a static magnetic field with the magnetic induction intensity of 2T, stirring the refined alloy liquid by using a stirring device, wherein the stirring speed is 1000r/min, the stirring time is 1h, and a nitrogen and argon mixed gas with the volume ratio of 2:1 is continuously introduced in the stirring process, wherein the stirring device comprises a stirring motor, a stirring shaft and a plurality of stirring blades which are sequentially connected, the stirring blades are arranged at equal intervals along the length direction of the stirring shaft, the stirring blades are parallel to each other, and neodymium iron boron magnets are attached to the surfaces of the stirring blades.
Preferably, in the fifth step, the mixed gas of carbon dioxide and sulfur hexafluoride with the volume ratio of 75:1 is continuously introduced for protection during the casting process.
Preferably, in the fifth step, the extrusion ratio is 30 and the extrusion speed is 20m/min when the extrusion operation is performed.
The invention at least comprises the following beneficial effects:
(1) the wrought magnesium alloy provided by the invention has good ductility, and can make up the defect that the application of the wrought magnesium alloy is limited due to insufficient ductility, wherein the added zinc, zirconium, lanthanum, yttrium and gadolinium elements can change the crystal structure of magnesium, avoid the formation of intermetallic compounds and refine the crystal grains of the magnesium alloy, and the barium, manganese, strontium and antimony can prevent the alloy elements from burning loss in the melting process, and can enhance the effects of the zinc, zirconium, lanthanum, yttrium and gadolinium elements to further refine the crystal grains of the magnesium alloy, so that the wrought magnesium alloy has higher ductility while maintaining excellent mechanical properties.
(2) In the preparation method provided by the invention, the aluminum-silicon intermediate alloy, the aluminum-boron intermediate alloy and the potassium fluoborate are added to further refine the crystal grains of the magnesium alloy so as to improve the strength and the ductility of the wrought magnesium alloy, and simultaneously, the magnetic field lines penetrate through the refined alloy liquid by using the stirring action of a static magnetic field and a magnet before the refined alloy liquid is poured, so that on one hand, the crystal phase structure in the refined alloy liquid can be changed to influence the growth process of crystal nuclei so as to further refine the crystal grains, on the other hand, the uniformity and the stability of the components of the refined alloy liquid can be improved, the precipitation phenomenon is avoided, and the alloy liquid with excellent properties is provided for the subsequent casting process, thereby effectively improving the ductility of the finally prepared wrought magnesium alloy.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples to enable those skilled in the art to practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
< example 1>
The wrought magnesium alloy with high ductility comprises the following raw materials in parts by weight: 83 parts of magnesium, 5 parts of aluminum, 1 part of zinc, 1 part of zirconium, 0.8 part of lanthanum, 0.8 part of yttrium, 0.8 part of gadolinium, 1.5 parts of calcium, 1 part of barium, 2 parts of manganese, 0.5 part of strontium and 0.3 part of antimony.
Magnesium is pure magnesium ingot, aluminum is pure aluminum ingot, zinc is pure zinc ingot, and the purity of zirconium, lanthanum, yttrium, gadolinium, calcium, barium, manganese, strontium and antimony is more than or equal to 99%.
The preparation method of the wrought magnesium alloy with high ductility specifically comprises the following steps: weighing magnesium and aluminum according to the weight parts, preheating at 100 ℃ for 3 hours, putting into a magnesium alloy furnace, covering the surfaces of the magnesium and the aluminum with mixed powder of graphite, calcium chloride and potassium chloride in a mass ratio of 1:2:2, introducing mixed gas of nitrogen and argon in a volume ratio of 2:1 into the magnesium alloy furnace, raising the temperature of the magnesium alloy furnace to melt the magnesium and the aluminum, stirring for 15 minutes, removing slag to obtain first alloy liquid, wherein the mixed powder of the graphite, the calcium chloride and the potassium chloride is subjected to ball milling for 5 hours at a rotating speed of 800r/min and a ball-to-material ratio of 4:1 before use, and is taken out and then passes through a 300-mesh screen; weighing zinc, zirconium, lanthanum, yttrium, gadolinium, calcium, barium, manganese, strontium and antimony according to the weight parts, respectively preheating for 3h at 150 ℃, then adding preheated calcium, barium, manganese, strontium and antimony into the first alloy liquid, heating, stirring for 15min after the calcium, barium, manganese, strontium and antimony are completely melted, adding preheated zinc, zirconium, lanthanum, yttrium and gadolinium, heating, stirring for 20min after the zinc, zirconium, lanthanum, yttrium and gadolinium are completely melted, and removing molten slag to obtain a second alloy liquid, wherein a mixed gas of nitrogen and argon is introduced in the whole melting process in a volume ratio of 2: 1; adding the preheated aluminum-silicon intermediate alloy into the second alloy liquid, heating, adding the preheated aluminum-boron intermediate alloy after the aluminum-silicon intermediate alloy is completely melted, heating, adding potassium fluoborate after the aluminum-boron intermediate alloy is completely melted, heating to 730 ℃, and stirring for ultrasonic 1h under the conditions that the ultrasonic frequency is 30KHz and the stirring speed is 1000r/min (the operation can be carried out in a magnesium alloy furnace with an ultrasonic stirring device, namely the middle part of the magnesium alloy furnace is provided with the stirring device, the inner wall is provided with the ultrasonic generating device) to obtain a third alloy liquid, wherein the adding amount of the aluminum-silicon intermediate alloy is 5 percent of the weight of the second alloy liquid, the adding amount of the aluminum-boron intermediate alloy is 0.8 percent of the weight of the second alloy liquid, and the adding amount of the potassium fluoborate is 2 percent of the weight of the second alloy liquid, continuously introducing a mixed gas of nitrogen and argon with the volume ratio of 2:1 in the whole melting and stirring process, wherein the preheating processes of the aluminum-silicon intermediate alloy and the aluminum-boron intermediate alloy both comprise the following steps: preheating for 3h at 150 ℃; heating the third alloy liquid to 760 ℃, adding a magnesium alloy refining agent under stirring at a stirring speed of 500r/min, refining for 1h, standing for 20min, and removing sediments to obtain refined alloy liquid, wherein the addition amount of the magnesium alloy refining agent is 5% of the weight of the third alloy liquid, and nitrogen and argon mixed gas with a volume ratio of 2:1 is continuously introduced in the refining process; and cooling the refined alloy liquid to 700 ℃, then casting into an ingot, tempering the ingot at 500 ℃ for 3h, cooling to 400 ℃ for extrusion to obtain a magnesium alloy plate, preserving the temperature of the magnesium alloy plate at 150 ℃ for 20h, and naturally cooling to obtain a high-ductility deformed magnesium alloy finished product.
The refining alloy liquid is refined after being cooled and before being cast, and the specific process of the refining treatment comprises the following steps: the method comprises the steps of placing refined alloy liquid in a static magnetic field with the magnetic induction intensity of 2T, stirring the refined alloy liquid by using a stirring device, wherein the stirring speed is 1000r/min, the stirring time is 1h, and a nitrogen and argon mixed gas with the volume ratio of 2:1 is continuously introduced in the stirring process, wherein the stirring device comprises a stirring motor, a stirring shaft and a plurality of stirring blades which are sequentially connected, the stirring blades are arranged at equal intervals along the length direction of the stirring shaft, the stirring blades are parallel to each other, and neodymium iron boron magnets are attached to the surfaces of the stirring blades.
And continuously introducing mixed gas of carbon dioxide and sulfur hexafluoride with the volume ratio of 75:1 for protection in the casting process.
In the extrusion operation, the extrusion ratio was 30 and the extrusion speed was 20 m/min.
To illustrate the effects of the present invention, the inventors provide comparative experiments as follows:
< comparative example 1>
The formulation and preparation method of wrought magnesium alloy with high ductility are the same as example 1, except that: zinc, zirconium, lanthanum, yttrium and gadolinium are not added.
< comparative example 2>
The formulation and preparation method of wrought magnesium alloy with high ductility are the same as example 1, except that: barium, manganese, strontium and antimony were not added.
< comparative example 3>
The formulation of wrought magnesium alloy with high ductility was the same as example 1, except that: the preparation process does not add aluminum-silicon intermediate alloy, aluminum-boron intermediate alloy and potassium fluoborate.
< comparative example 4>
The formulation of wrought magnesium alloy with high ductility was the same as example 1, except that: the refined alloy liquid is directly cast after being cooled, and the refining treatment is not carried out.
Method for evaluating ductility of wrought magnesium alloy: the elongation and grain size of the wrought magnesium alloy finished product were measured, and the results are shown in table 1 below.
The method for evaluating the mechanical property of the wrought magnesium alloy comprises the following steps: the tensile strength and yield strength of the wrought magnesium alloy finished product were measured, and the results are shown in table 2 below.
[ Table 1]
[ Table 2]
| Group of | Tensile strength (MPa) | Yield strength (MPa) |
| Example 1 | 301 | 224 |
| Comparative example 1 | 219 | 138 |
| Comparative example 2 | 238 | 149 |
| Comparative example 3 | 257 | 168 |
| Comparative example 4 | 208 | 122 |
As can be seen from tables 1 and 2 above, the elongation of example 1 is maximized, the grain size is minimized, and the tensile strength and yield strength are maximized, which indicates that the wrought magnesium alloy prepared in example 1 has the highest ductility and the most excellent mechanical properties, and is the best example.
Comparative example 1 compared with example 1, the formulation and preparation method of wrought magnesium alloy with high ductility are the same, except that: no zinc, zirconium, lanthanum, yttrium and gadolinium were added. As can be seen from the above tables 1 and 2, compared with the example 1, the ductility and the mechanical properties of the comparative example 1 are both reduced, mainly because the zinc, zirconium, lanthanum, yttrium and gadolinium elements can change the crystal structure of magnesium, avoid forming intermetallic compounds, refine the crystal grains of the magnesium alloy, and the size of the crystal grains in the metal material has a great influence on the properties of the metal material, and the strength, hardness, plasticity and toughness of the metal material are all improved along with the reduction of the size of the crystal grains, so that after the crystal grains are refined, the size of the crystal grains is obviously reduced, and the ductility and the mechanical properties of the deformed magnesium alloy are also obviously improved.
Comparative example 2 compared with example 1, the formulation and preparation method of wrought magnesium alloy with high ductility are the same, except that: barium, manganese, strontium and antimony were not added. As can be seen from the above tables 1 and 2, compared with the example 1, the ductility and the mechanical properties of the comparative example 2 are both reduced, which is mainly because the barium, the manganese, the strontium and the antimony can prevent the alloy elements from burning loss in the melting process, resulting in non-ideal alloy proportion and reduced mechanical properties, and can enhance the effects of the zinc, the zirconium, the lanthanum, the yttrium and the gadolinium elements, so as to further refine the crystal grains of the magnesium alloy, thereby enabling the wrought magnesium alloy to have higher ductility while maintaining excellent mechanical properties.
Comparative example 3 a wrought magnesium alloy having high ductility was formulated identically to example 1, except that: the preparation process did not add aluminum-silicon master alloy, aluminum-boron master alloy and potassium fluoborate. As can be seen from the above tables 1 and 2, the ductility and mechanical properties of comparative example 3 are reduced as compared to example 1, mainly because the aluminum-silicon master alloy, the aluminum-boron master alloy, and the potassium fluoroborate can further refine the crystal grains of the magnesium alloy to improve the strength and ductility of the wrought magnesium alloy.
Comparative example 4 a wrought magnesium alloy having high ductility was formulated identically to example 1, except that: the refined alloy liquid is directly cast after being cooled, and is not subjected to refining treatment. As can be seen from the above tables 1 and 2, the ductility and the mechanical properties of the wrought magnesium alloy obtained in comparative example 4 are both reduced, mainly because the magnetic field lines can penetrate through the refined alloy liquid under the action of the static magnetic field and the magnetic stirring, which can change the internal crystalline phase structure of the refined alloy liquid, affect the growth process of crystal nuclei, further refine crystal grains, improve the uniformity and stability of the components of the refined alloy liquid, avoid the precipitation phenomenon, provide an alloy liquid with excellent properties for the subsequent casting process, and thus effectively improve the ductility and the mechanical properties of the finally prepared wrought magnesium alloy.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the examples shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (5)
1. The wrought magnesium alloy with high ductility is characterized by comprising the following raw materials in parts by weight: 83 parts of magnesium, 5 parts of aluminum, 1 part of zinc, 1 part of zirconium, 0.8 part of lanthanum, 0.8 part of yttrium, 0.8 part of gadolinium, 1.5 parts of calcium, 1 part of barium, 2 parts of manganese, 0.5 part of strontium and 0.3 part of antimony;
the preparation method of the wrought magnesium alloy with high ductility comprises the following steps:
the method comprises the following steps: weighing magnesium and aluminum according to the weight parts, preheating at 100 ℃ for 3 hours, putting into a magnesium alloy furnace, covering the surfaces of the magnesium and the aluminum with mixed powder of graphite, calcium chloride and potassium chloride in a mass ratio of 1:2:2, introducing mixed gas of nitrogen and argon in a volume ratio of 2:1 into the magnesium alloy furnace, raising the temperature of the magnesium alloy furnace to melt the magnesium and the aluminum, stirring for 15 minutes, removing slag to obtain first alloy liquid, wherein the mixed powder of the graphite, the calcium chloride and the potassium chloride is subjected to ball milling for 5 hours at a rotating speed of 800r/min and a ball-to-material ratio of 4:1 before use, and is taken out and then passes through a 300-mesh screen;
step two: weighing zinc, zirconium, lanthanum, yttrium, gadolinium, calcium, barium, manganese, strontium and antimony according to the weight parts, respectively preheating for 3 hours at 150 ℃, then adding preheated calcium, barium, manganese, strontium and antimony into the first alloy liquid prepared in the step one, heating, stirring for 15 minutes after the calcium, barium, manganese, strontium and antimony are completely melted, then adding preheated zinc, zirconium, lanthanum, yttrium and gadolinium, heating, stirring for 20 minutes after the zinc, zirconium, lanthanum, yttrium and gadolinium are completely melted, and removing molten slag to obtain a second alloy liquid, wherein a mixed gas of nitrogen and argon with a volume ratio of 2:1 is introduced in the whole melting process;
step three: adding the preheated aluminum-silicon intermediate alloy into the second alloy liquid prepared in the step two, heating, after the aluminum-silicon intermediate alloy is completely melted, adding preheated Al-B intermediate alloy, heating until the Al-B intermediate alloy is completely molten, adding potassium fluoborate, heating to 730 ℃, placing under the conditions that the ultrasonic frequency is 30KHz and the stirring speed is 1000r/min, stirring and ultrasonic treating for 1h to obtain a third alloy liquid, wherein the adding amount of the aluminum-silicon intermediate alloy is 5 percent of the weight of the second alloy liquid, the adding amount of the aluminum-boron intermediate alloy is 0.8 percent of the weight of the second alloy liquid, the adding amount of the potassium fluoborate is 2 percent of the weight of the second alloy liquid, continuously introducing a mixed gas of nitrogen and argon with the volume ratio of 2:1 in the whole melting and stirring process, wherein the preheating processes of the aluminum-silicon intermediate alloy and the aluminum-boron intermediate alloy both comprise the following steps: preheating for 3h at 150 ℃;
step four: heating the third alloy liquid prepared in the third step to 760 ℃, then adding a magnesium alloy refining agent under stirring at a stirring speed of 500r/min, refining for 1h, standing for 20min, and finally removing sediments to obtain refined alloy liquid, wherein the addition amount of the magnesium alloy refining agent is 5% of the weight of the third alloy liquid, and a mixed gas of nitrogen and argon with a volume ratio of 2:1 is continuously introduced in the refining process;
step five: and cooling the refined alloy liquid prepared in the fourth step to 700 ℃, then casting into a cast ingot, tempering the cast ingot at 500 ℃ for 3h, cooling to 400 ℃ for extrusion to prepare a magnesium alloy sheet, preserving the heat of the magnesium alloy sheet at 150 ℃ for 20h, and then naturally cooling to prepare a high-ductility deformed magnesium alloy finished product.
2. The wrought magnesium alloy with high ductility according to claim 1, wherein the magnesium is pure magnesium ingot, the aluminum is pure aluminum ingot, the zinc is pure zinc ingot, and the zirconium, lanthanum, yttrium, gadolinium, calcium, barium, manganese, strontium, and antimony are all at a purity of 99% or more.
3. A method for preparing a wrought magnesium alloy with high ductility according to claim 1, comprising the steps of:
the method comprises the following steps: weighing magnesium and aluminum according to the weight parts, preheating at 100 ℃ for 3 hours, putting into a magnesium alloy furnace, covering the surfaces of the magnesium and the aluminum with mixed powder of graphite, calcium chloride and potassium chloride in a mass ratio of 1:2:2, introducing mixed gas of nitrogen and argon in a volume ratio of 2:1 into the magnesium alloy furnace, raising the temperature of the magnesium alloy furnace to melt the magnesium and the aluminum, stirring for 15 minutes, removing slag to obtain first alloy liquid, wherein the mixed powder of the graphite, the calcium chloride and the potassium chloride is subjected to ball milling for 5 hours at a rotating speed of 800r/min and a ball-to-material ratio of 4:1 before use, and is taken out and then passes through a 300-mesh screen;
step two: weighing zinc, zirconium, lanthanum, yttrium, gadolinium, calcium, barium, manganese, strontium and antimony according to the weight parts, respectively preheating for 3 hours at 150 ℃, then adding preheated calcium, barium, manganese, strontium and antimony into the first alloy liquid prepared in the step one, heating, stirring for 15 minutes after the calcium, barium, manganese, strontium and antimony are completely melted, then adding preheated zinc, zirconium, lanthanum, yttrium and gadolinium, heating, stirring for 20 minutes after the zinc, zirconium, lanthanum, yttrium and gadolinium are completely melted, and removing molten slag to obtain a second alloy liquid, wherein a mixed gas of nitrogen and argon with a volume ratio of 2:1 is introduced in the whole melting process;
step three: adding the preheated aluminum-silicon intermediate alloy into the second alloy liquid prepared in the step two, heating, after the aluminum-silicon intermediate alloy is completely melted, adding preheated Al-B intermediate alloy, heating until the Al-B intermediate alloy is completely molten, adding potassium fluoborate, heating to 730 ℃, placing under the conditions that the ultrasonic frequency is 30KHz and the stirring speed is 1000r/min, stirring and ultrasonic treating for 1h to obtain a third alloy liquid, wherein the adding amount of the aluminum-silicon intermediate alloy is 5 percent of the weight of the second alloy liquid, the adding amount of the aluminum-boron intermediate alloy is 0.8 percent of the weight of the second alloy liquid, the adding amount of the potassium fluoborate is 2 percent of the weight of the second alloy liquid, continuously introducing a mixed gas of nitrogen and argon with the volume ratio of 2:1 in the whole melting and stirring process, wherein the preheating processes of the aluminum-silicon intermediate alloy and the aluminum-boron intermediate alloy both comprise the following steps: preheating for 3h at 150 ℃;
step four: heating the third alloy liquid prepared in the third step to 760 ℃, then adding a magnesium alloy refining agent under stirring at a stirring speed of 500r/min, refining for 1h, standing for 20min, and finally removing sediments to obtain refined alloy liquid, wherein the addition amount of the magnesium alloy refining agent is 5% of the weight of the third alloy liquid, and a mixed gas of nitrogen and argon with a volume ratio of 2:1 is continuously introduced in the refining process;
step five: cooling the refined alloy liquid prepared in the fourth step to 700 ℃, then casting the refined alloy liquid into a cast ingot, tempering the cast ingot at 500 ℃ for 3h, cooling the cast ingot to 400 ℃ for extrusion to prepare a magnesium alloy sheet, and naturally cooling the magnesium alloy sheet after the magnesium alloy sheet is kept at 150 ℃ for 20h to prepare a deformed magnesium alloy finished product with high ductility;
in the fifth step, the refined alloy liquid is refined after being cooled and before being cast, and the specific process of the refining treatment comprises the following steps: the method comprises the steps of placing refined alloy liquid in a static magnetic field with the magnetic induction intensity of 2T, stirring the refined alloy liquid by using a stirring device, wherein the stirring speed is 1000r/min, the stirring time is 1h, and a nitrogen and argon mixed gas with the volume ratio of 2:1 is continuously introduced in the stirring process, wherein the stirring device comprises a stirring motor, a stirring shaft and a plurality of stirring blades which are sequentially connected, the stirring blades are arranged at equal intervals along the length direction of the stirring shaft, the stirring blades are parallel to each other, and neodymium iron boron magnets are attached to the surfaces of the stirring blades.
4. The method for preparing wrought magnesium alloy with high ductility according to claim 3, wherein in the fifth step, the mixed gas of carbon dioxide and sulfur hexafluoride with volume ratio of 75:1 is continuously introduced for protection during the casting process.
5. The method of manufacturing a wrought magnesium alloy with high ductility according to claim 3, wherein in the fifth step, the extrusion rate is 30 and the extrusion speed is 20m/min at the time of the extrusion operation.
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| CN102776421A (en) * | 2012-08-15 | 2012-11-14 | 深圳市新星轻合金材料股份有限公司 | Alloy for refinement of magnesium and alloy grain thereof and preparation method of alloy |
| CN108677074A (en) * | 2018-05-02 | 2018-10-19 | 王甲林 | A kind of medical degradable corrosion-resistant magnesium alloy bracket and preparation method thereof of implantation heart |
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| CN101985714A (en) * | 2010-12-07 | 2011-03-16 | 吉林大学 | High-plasticity magnesium alloy and preparation method thereof |
| CN102776421A (en) * | 2012-08-15 | 2012-11-14 | 深圳市新星轻合金材料股份有限公司 | Alloy for refinement of magnesium and alloy grain thereof and preparation method of alloy |
| CN108677074A (en) * | 2018-05-02 | 2018-10-19 | 王甲林 | A kind of medical degradable corrosion-resistant magnesium alloy bracket and preparation method thereof of implantation heart |
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