CN117758092A - Magnesium-titanium intermediate alloy, preparation method thereof and magnesium-titanium alloy - Google Patents
Magnesium-titanium intermediate alloy, preparation method thereof and magnesium-titanium alloy Download PDFInfo
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- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 64
- 239000000956 alloy Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 11
- 239000011777 magnesium Substances 0.000 claims abstract description 79
- -1 alkali metal salt Chemical class 0.000 claims abstract description 77
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 75
- 238000003723 Smelting Methods 0.000 claims abstract description 68
- 239000010936 titanium Substances 0.000 claims abstract description 53
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000003608 titanium Chemical class 0.000 claims abstract description 48
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 46
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 42
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 31
- 238000005266 casting Methods 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 229910018503 SF6 Inorganic materials 0.000 claims description 15
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 15
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 11
- 159000000000 sodium salts Chemical class 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 9
- 159000000003 magnesium salts Chemical group 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002923 metal particle Substances 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229960005419 nitrogen Drugs 0.000 claims description 3
- 229960004424 carbon dioxide Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 40
- 150000003839 salts Chemical class 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 18
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004062 sedimentation Methods 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 description 13
- 229910000861 Mg alloy Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000155 melt Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 239000002893 slag Substances 0.000 description 10
- 238000005498 polishing Methods 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 231100000719 pollutant Toxicity 0.000 description 8
- 230000009467 reduction Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a magnesium-titanium intermediate alloy, a preparation method thereof and a magnesium-titanium alloy; the preparation method of the magnesium-titanium intermediate alloy comprises the following steps: mixing and smelting metal magnesium, titanium salt, alkali metal salt and alkaline earth metal salt, and forming; wherein the mass ratio of the metal magnesium, the titanium salt, the alkali metal salt and the alkaline earth metal salt is 1 (0.4-2.3): 0.5-2.6): 0-1. According to the method, the reducing molten salt environment is provided, so that the titanium salt is promoted to be reduced into the metal titanium particles with smaller particle size, the sedimentation speed of the metal titanium particles in the magnesium melt is reduced, and the metal titanium particles are uniformly distributed in the magnesium melt; meanwhile, the titanium content in the magnesium-titanium intermediate alloy is further improved by controlling the use amount of the raw material components, so that the grain refinement effect of the magnesium-titanium intermediate alloy is further improved, and the performance of the magnesium-titanium intermediate alloy is improved. In addition, the reducing molten salt can cover the fused mass of the metal magnesium to prevent the fused mass of the metal magnesium from burning, thereby improving the safety of the process.
Description
Technical Field
The invention relates to the field of alloys, in particular to a magnesium-titanium intermediate alloy, a preparation method thereof and a magnesium-titanium alloy.
Background
The magnesium alloy has the characteristics of low density, good damping vibration attenuation, heat conductivity, electromagnetic shielding property, abundant resource reserves, easy recycling and reproduction and the like, is an ideal structural functional material under the background of low-carbon green development, and has wide application prospect in the fields of aviation, aerospace, automobiles, electronics and the like. At present, the magnesium alloy has the disadvantages of low strength, difficult deformation processing, high production cost, low yield and the like, and limits the application and development of the magnesium alloy. The fine grain strengthening is a strengthening means for effectively improving the strength and the processing performance of the magnesium alloy, and has important significance for developing and applying the magnesium alloy by developing a high-efficiency magnesium alloy grain refiner.
The addition of part of alloy elements in magnesium alloy can refine grains, improve structure and performance. Ti has the property in magnesium alloy, so that Ti element has great potential as magnesium alloy grain refinement element. Ti has good effect of inhibiting grain growth, and GRF (Growth restriction factor) is 59500. In addition, the crystal structures of Ti and Mg are uniformly and densely arranged in a hexagonal manner, the lattice constant (a=0.292 nm, c=0.468 nm) of α -Ti is similar to that of Mg (a=0.321 nm, c=0.521 nm), the lattice mismatch degree is low, and the wettability of magnesium and titanium is good. Therefore, ti has good grain refinement effect on magnesium alloy.
Although Ti element has great potential, ti is easy to deposit by directly adding Ti particles into a magnesium melt because of larger difference of melting points of Mg and Ti and larger difference of densities of Ti and Mg, and the distribution of Ti in the obtained magnesium-titanium alloy intermediate is uneven. And since the solid solubility of Ti in Mg is low, for example, the solid solubility of Ti in Mg is 0.19wt% at 650 ℃; the solid solubility of Ti in Mg at 350 ℃ is 0.08wt%, and is difficult to be effectively added into magnesium alloy, thus being unfavorable for improving the grain refinement effect of the magnesium alloy.
Disclosure of Invention
Based on the above, it is necessary to provide a magnesium-titanium intermediate alloy with higher titanium content and more uniform distribution, a preparation method thereof and a magnesium-titanium alloy.
The invention provides a preparation method of a magnesium-titanium intermediate alloy, which is characterized by comprising the following steps of:
mixing and smelting metal magnesium, titanium salt, alkali metal salt and alkaline earth metal salt, and forming; wherein the mass ratio of the metal magnesium to the titanium salt to the alkali metal salt to the alkaline earth metal salt is 1 (0.4-2.3): 0.5-2.6): 0-1.
According to the preparation method, the metal element titanium is provided by the titanium salt, and the alkali metal salt and the alkaline earth metal salt are added in the smelting process to provide a reducing molten salt environment for the smelting process, so that the titanium salt is promoted to be reduced into the metal titanium particles with smaller particle size, the sedimentation speed of the metal titanium particles in the magnesium melt is reduced, the metal titanium particles are uniformly distributed in the magnesium melt, and the magnesium-titanium intermediate alloy with uniform titanium distribution is further obtained. Meanwhile, the reduction degree of titanium salt in the magnesium melt can be further controlled by controlling the consumption of the raw material components, so that the titanium content in the magnesium-titanium intermediate alloy is improved, the grain refinement effect of the magnesium-titanium intermediate alloy is further improved, and the performance of the magnesium-titanium intermediate alloy is improved. In addition, the reducing molten salt can cover the fused mass of the metal magnesium to prevent the fused mass of the metal magnesium from burning, thereby improving the safety of the process.
In some embodiments, the titanium salt comprises potassium titanate, titanium chloride and titanium fluoride in a mass ratio of 1 (0-1): 0-1; and/or the number of the groups of groups,
the alkali metal salt comprises potassium salt and sodium salt with the mass ratio of (0.5-1.8) to (0-0.8); and/or the number of the groups of groups,
the alkaline earth metal salt is magnesium salt; and/or the number of the groups of groups,
the metal magnesium is magnesium ingot.
In some embodiments, the potassium salt comprises potassium chloride and potassium fluoride in a mass ratio of (0.6-1): 0-1; and/or the number of the groups of groups,
the sodium salt is at least one of sodium chloride and sodium fluoride; and/or the number of the groups of groups,
the magnesium salt is at least one selected from magnesium chloride and magnesium fluoride.
In some embodiments, the ratio of the mass of the magnesium ingot, the titanium salt, the alkali metal salt, and the alkaline earth metal salt is 1 (1.4-2.3): 1.8-2.6): 0.3-0.75.
In some embodiments, the smelting is performed under a protective atmosphere; the protective gas in the protective atmosphere is selected from two mixed gases of argon, carbon dioxide, sulfur hexafluoride, nitrogen and sulfur hexafluoride.
In some embodiments, the smelting is performed under mechanical or manual stirring at a speed of 30r/min to 500r/min; or,
the smelting is carried out under electromagnetic stirring, the stirring power of the electromagnetic stirring is 30kW-100Kw, and the stirring frequency is 80Hz-800Hz.
In some embodiments, the molding includes casting and cooling molding steps, the casting being performed under electromagnetic vibration conditions, the electromagnetic vibration frequency being 200Hz to 500Hz.
The second aspect of the invention provides a magnesium-titanium intermediate alloy, which is prepared according to the preparation method.
In some embodiments, the magnesium-titanium master alloy comprises 65wt% to 95wt% of magnesium element and 5wt% to 35wt% of titanium element in terms of mass percent; and/or the average grain diameter of the titanium metal particles in the magnesium-titanium master alloy is 1-20 mu m.
The third aspect of the invention provides a magnesium-titanium alloy, which is prepared from the magnesium-titanium intermediate alloy.
Drawings
FIG. 1 is a microstructure of magnesium-titanium master alloy prepared in example 2.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention, and preferred embodiments of the present invention are set forth. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. It should be understood that these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In one embodiment of the invention, a preparation method of a magnesium-titanium intermediate alloy is provided, which comprises the following steps:
mixing and smelting metal magnesium, titanium salt, alkali metal salt and alkaline earth metal salt, and forming; wherein the mass ratio of the metal magnesium, the titanium salt, the alkali metal salt and the alkaline earth metal salt is 1 (0.4-2.3): 0.5-2.6): 0-1.
According to the preparation method, the metal element titanium is provided by the titanium salt, and the alkali metal salt and the alkaline earth metal salt are added in the smelting process to provide a reducing molten salt environment for the smelting process, so that the titanium salt is promoted to be reduced into the metal titanium particles with smaller particle size, the sedimentation speed of the metal titanium particles in the magnesium melt is reduced, the metal titanium particles are uniformly distributed in the magnesium melt, and the magnesium-titanium intermediate alloy with uniform titanium distribution is further obtained. Meanwhile, the reduction degree of titanium salt in the magnesium melt can be further controlled by controlling the consumption of the raw material components, so that the titanium content in the magnesium-titanium intermediate alloy is improved, the grain refinement effect of the magnesium-titanium intermediate alloy is further improved, and the performance of the magnesium-titanium intermediate alloy is improved. In addition, the reducing molten salt can cover the fused mass of the metal magnesium to prevent the fused mass of the metal magnesium from burning, thereby improving the safety of the process.
When the mass ratio of alkaline earth metal salt is taken to be 0, the alkali metal salt in the method provides a reducing molten salt environment for the smelting process, and promotes the reduction of titanium salt into metal titanium particles with smaller particle size. The preparation method comprises the steps of mixing and smelting magnesium metal, titanium salt and alkali metal salt, and then forming.
Further, the mass ratio of the metal magnesium, the titanium salt, the alkali metal salt and the alkaline earth metal salt is 1 (0.4-2.3): 0.5-2.6): 0.1-1.
Further, the mass ratio of the metal magnesium, the titanium salt, the alkali metal salt and the alkaline earth metal salt is 1 (1.4-2.3): 1.8-2.6): 0.3-0.75.
In some embodiments, the titanium salt comprises potassium titanate, titanium chloride, and titanium fluoride in a mass ratio of 1 (0-1): 0-1. Wherein, when the mass ratio of titanium chloride to titanium fluoride is 0, it means that the titanium salt includes potassium titanate and does not include titanium chloride and titanium fluoride. When the ratio of the mass of titanium chloride is 0 and the ratio of the mass of titanium fluoride is not 0, it means that the titanium salt includes potassium titanate and titanium fluoride, but does not include titanium chloride; when the ratio of the mass of titanium chloride to the mass of titanium fluoride is not 0 and the ratio of the mass of titanium fluoride to the mass of titanium fluoride is 0, it means that the titanium salt includes potassium titanate and titanium chloride, and does not include titanium fluoride.
Further, the titanium salt comprises potassium titanate, titanium chloride and titanium fluoride with the mass ratio of (0.6-1): (0.3-0.5): (0.3-0.7).
In some embodiments, the alkali metal salt comprises potassium and sodium salts in a mass ratio of (0.5-2.0): 0-0.8. When the mass ratio of the sodium salt is 0, it means that the alkali metal salt includes the potassium salt, and does not contain the sodium salt. Further, the mass ratio of the potassium salt to the sodium salt in the alkali metal salt is (1.3-2.0): 0.3-0.8.
In some embodiments, the potassium salt comprises potassium chloride and potassium fluoride in a mass ratio of (0.6-1.2): 0-1. When the mass ratio of potassium fluoride is 0, it means that the potassium salt includes potassium chloride and does not include potassium fluoride. Further, the potassium salt includes potassium chloride and potassium fluoride in a mass ratio of (0.7-1.2): 0.6-0.8.
In some embodiments, the sodium salt is selected from at least one of potassium chloride and sodium chloride.
In some embodiments, the sodium salt comprises sodium chloride and sodium fluoride in a mass ratio of (01-1): 0.1-1. Further, the sodium salt comprises sodium chloride and sodium fluoride in a mass ratio of (0.2-0.45): 0.1-0.4.
In some embodiments, alkaline earth metal salts include, but are not limited to, magnesium salts.
In some embodiments, the magnesium salt is selected from at least one of magnesium chloride and magnesium fluoride.
In some embodiments, the magnesium salt is magnesium chloride and magnesium fluoride in a mass ratio of (0.1-1): 0.1-1. Further, the magnesium salt comprises magnesium chloride and magnesium fluoride in a mass ratio of (0.1-0.3): 0.2-0.45.
In some embodiments, the average particle size of the titanium salt is from 0.1mm to 0.5mm.
In some embodiments, the alkali metal salt has an average particle size of 0.1mm to 1mm.
In some embodiments, the alkaline earth metal salt has an average particle size of 0.1mm to 1mm.
The average particle size of the titanium salt, the alkali metal salt and the alkaline earth metal salt in each raw material is controlled, so that the particles can be more favorable for forming melt, the reaction rate is accelerated, the smelting time is reduced, and the magnesium burning loss is reduced.
In some embodiments, the smelting temperature is 850 ℃ -1100 ℃. It is understood that the smelting temperature is 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ or 1100 ℃. Further, the melting temperature may be a range of values including any two of the above-mentioned point values. Preferably, the smelting temperature is 900-1000 ℃. By controlling the smelting temperature, the metal magnesium, the titanium salt, the alkali metal salt and the alkaline earth metal salt can be ensured to be fused into a melt, and the volatilization of the metal magnesium melt is reduced.
In some embodiments, the time of smelting is 15min-60min.
In some embodiments, smelting is performed under a protective atmosphere.
In some embodiments, the protective gas in the protective atmosphere is selected from two mixed gases of argon, sulfur hexafluoride, nitrogen, and sulfur hexafluoride.
In some embodiments, the protective gas is nitrogen and sulfur hexafluoride in a volume ratio of (95-99): 1-5.
In some embodiments, the protective gas is argon and sulfur hexafluoride in a volume ratio of (95-99): 1-5.
In some embodiments, the smelting is performed under electromagnetic stirring with a stirring power of 30kW-100kW and a stirring frequency of 80Hz-800Hz. Stirring is carried out in the smelting process, which is favorable for further preventing titanium metal particles generated by reduction from precipitating in the melt and further improving the distribution uniformity of the titanium metal particles in the magnesium-titanium intermediate alloy.
In some embodiments, smelting is performed with mechanical or manual stirring at a speed of 30r/min to 500r/min. It is understood that the stirring speed may be 30r/min, 50r/min, 100r/min, 200r/min, 300r/min, 400r/min or 500r/min. Further, the speed of agitation may be a range of values between any two of the above-mentioned point values. Further, the stirring speed is 60r/min-250r/min.
In some embodiments, stirring is continuous or batch stirring. Continuous stirring means stirring is carried out in the process of mixing smelting, and stirring is not stopped until the molding step is carried out. The intermittent stirring method is that after the pretreated metallic titanium particles are added into the magnesium melt, stirring is carried out once every 10min-20min, the stirring time is 5min-7min each time, and the stirring is stopped until the molding step is carried out.
In some embodiments, smelting is performed in a smelting furnace in which a smelting crucible height to diameter ratio is in the range of 1 (0.25-0.6). The control of the height-diameter ratio of the smelting crucible is beneficial to controlling the coverage amount of the reducing molten salt on the surface of the magnesium melt in the reaction process, and further prevents the burning and volatilization of the magnesium melt.
In some embodiments, the surface polishing treatment of the magnesium metal is included before the mixed smelting of the magnesium metal, the titanium salt, the alkali metal salt, and the alkaline earth metal salt. The surface polishing treatment of the magnesium metal can remove oxide skin and surface pollutants on the surface, and reduce the impurity content in the magnesium-titanium intermediate alloy.
In some embodiments, the method further comprises preheating the magnesium, titanium, alkali metal and alkaline earth metal salts prior to the mixing and smelting. The titanium salt, alkali metal salt and alkaline earth metal salt are preheated to remove water in the salts, which is beneficial to the reaction.
In some embodiments, the temperature of the preheating treatment is from 100 ℃ to 200 ℃.
In some embodiments, the time of the pre-heat treatment is 30min-100min.
In some embodiments, the shaping includes casting and cooling shaping steps.
In some embodiments, the casting step is performed under electromagnetic vibration conditions, the electromagnetic vibration frequency being 200Hz to 500Hz.
In some embodiments, the melt in the melting furnace is cast through a fine mesh filter screen into an electromagnetic vibration casting system. Larger impurities or titanium metal particles can be further filtered through the fine pore filter screen.
In some embodiments, the pore size of the fine pore filter is 20 mesh to 60 mesh.
In some embodiments, prior to the casting step, a step of removing slag is also included. The slag is mainly removed by removing residual alkali metal-containing substances and alkaline earth metal-containing substances after the reaction covered by the upper layer of the magnesium melt, thereby further reducing the impurity content in the magnesium-titanium intermediate alloy.
In some embodiments, after the slag removal step and before the casting step, a step of reducing the temperature of the melt is further included, and the casting step is initiated when the temperature of the melt is reduced to 800-1050 ℃.
In one embodiment of the present invention, a magnesium-titanium intermediate alloy is provided, which is obtained by the above-described preparation method.
In some embodiments, the magnesium-titanium master alloy comprises 65wt% to 95wt% of magnesium element and 5wt% to 35wt% of titanium element in terms of mass percent.
In some embodiments, the average particle size of the titanium metal particles in the magnesium-titanium master alloy is 1 μm to 20 μm.
In one embodiment of the invention, a magnesium-titanium alloy is provided, and the preparation raw material of the magnesium-titanium alloy comprises the magnesium-titanium intermediate alloy.
In order to make the objects, technical solutions and advantages of the present invention more concise, the present invention will be described in the following specific examples, but the present invention is by no means limited to these examples. The following examples are only preferred embodiments of the present invention, which can be used to describe the present invention, and should not be construed as limiting the scope of the invention. It should be noted that any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
In order to better illustrate the present invention, the following description of the present invention will be given with reference to examples. The following are specific examples.
Example 1
(1) Weighing magnesium ingots, titanium salts, alkali metal salts and alkaline earth metal salts according to the formula shown in table 1, wherein the average particle size of the titanium salts is 0.3mm; the average particle diameter of the alkali metal salt was 0.5mm.
(2) And (3) carrying out surface polishing treatment on the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 150deg.C for 30min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.25. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of nitrogen and sulfur hexafluoride, and the proportion is 99:1. the smelting temperature is 950 ℃ and the smelting time is 40min. Mechanical stirring is carried out in the smelting process; the rotational speed of the mechanical stirring is 300r/min.
(5) And (3) removing slag, cooling to a temperature of 850 ℃, enabling the melt to enter a casting die in an electromagnetic vibration casting die system through a fine pore filter screen, keeping electromagnetic vibration when casting, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element is Fe, cu, ni, si:0.036wt%.
Example 2
(1) Weighing magnesium ingots, titanium salts, alkali metal salts and alkaline earth metal salts according to the formula shown in table 1, wherein the average particle size of the titanium salts is 0.3mm; the average particle diameter of the alkali metal salt was 0.5mm.
(2) And (3) carrying out surface polishing treatment on the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 150deg.C for 30min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.6. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of nitrogen and sulfur hexafluoride, and the proportion is 99:1. the smelting temperature is 950 ℃ and the smelting time is 40min. Mechanical stirring is carried out in the smelting process; the rotational speed of the mechanical stirring is 300r/min.
(5) And (3) removing slag, cooling to a temperature of 850 ℃, enabling the melt to enter a casting die in an electromagnetic vibration casting die system through a fine pore filter screen, keeping electromagnetic vibration when casting, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element is Fe, cu, ni, si:0.036wt%.
Example 3
(1) Weighing magnesium ingot, titanium salt, alkali metal salt and alkaline earth metal salt according to the formula shown in Table 1, wherein the average particle size of the titanium salt is 0.3mm; the average particle diameter of the alkali metal salt was 0.5mm.
(2) And (3) polishing the surface of the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 120deg.C for 40min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.4. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of nitrogen and sulfur hexafluoride, and the proportion is 99:1. the smelting temperature is 950 ℃ and the smelting time is 15min. In the smelting process, an electromagnetic oven is stirred, the stirring power of the electromagnetic oven is 90kW, and the stirring frequency is 110.
(5) And (3) removing slag, cooling to 900 ℃, enabling the melt to enter a casting die in an electromagnetic vibration casting die system through a fine pore filter screen, keeping electromagnetic vibration when casting, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element Fe, cu, ni, si: 0.025wt%.
Example 4
(1) Magnesium ingots, titanium salts, alkali metal salts, and alkaline earth metal salts were weighed according to the formulation shown in table 1. Wherein the average particle diameter of the titanium salt is 0.1mm; the average particle diameter of the alkali metal salt was 0.3mm.
(2) And (3) polishing the surface of the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 120deg.C for 40min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.3. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of nitrogen and sulfur hexafluoride, and the proportion is 99:1. the smelting temperature is 1050 ℃, and the smelting time is 15min. In the smelting process, an electromagnetic oven is stirred, the stirring power of the electromagnetic oven is 95kW, and the stirring frequency is 400Hz.
(5) And (3) removing slag, cooling to 950 ℃, enabling the melt to enter a casting die in an electromagnetic vibration casting die system through a fine pore filter screen, keeping electromagnetic vibration when casting, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element is Fe, cu, ni, si:0.038wt%.
Example 5
(1) Magnesium ingots, titanium salts, alkali metal salts, and alkaline earth metal salts were weighed according to the formulation shown in table 1. Wherein the average grain diameter of the titanium salt is 0.3mm; the average particle diameter of the alkali metal salt was 0.5mm.
(2) And (3) polishing the surface of the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 100deg.C for 40min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.4. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of nitrogen and sulfur hexafluoride, and the proportion is 99:1. the smelting temperature is 850 ℃ and the smelting time is 60min. Mechanical stirring is carried out in the smelting process; the rotational speed of the mechanical stirring is 50r/min.
(5) And (3) removing slag, cooling to 800 ℃, pouring the melt into a mould through a fine pore filter screen, wherein the electromagnetic vibration frequency is 300Hz, maintaining electromagnetic vibration during pouring, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element is Fe, cu, ni, si:0.014wt%.
Example 6
(1) Magnesium ingots, titanium salts, alkali metal salts, and alkaline earth metal salts were weighed according to the formulation shown in table 1. Wherein the average grain diameter of the titanium salt is 0.2mm; the average particle diameter of the alkali metal salt was 1mm.
(2) And (3) polishing the surface of the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 100deg.C for 50min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.5. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of argon and sulfur hexafluoride, and the proportion is 96:4. the smelting reduction temperature is 950 ℃ and the smelting time is 30min. Mechanical stirring is carried out in the smelting process; the rotational speed of the mechanical stirring is 450r/min.
(5) And (3) removing slag, cooling to 900 ℃, enabling the melt to enter a casting die of an electromagnetic vibration casting die system through a fine pore filter screen, keeping electromagnetic vibration when casting, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element is Fe, cu, ni, si:0.055wt%.
Example 7
(1) Magnesium ingots, titanium salts, alkali metal salts, and alkaline earth metal salts were weighed according to the formulation shown in table 1. Wherein the average grain diameter of the titanium salt is 0.2mm; the average particle diameter of the alkali metal salt was 1mm.
(2) And (3) polishing the surface of the magnesium ingot to remove oxide scales and surface pollutants.
(3) Preheating the above salts at 100deg.C for 50min to obtain preheated salt.
(4) Adding the magnesium ingot and salt treated in the step (2) and the step (3) into a smelting furnace, wherein the height-to-diameter ratio of a crucible is 1:0.5. smelting under the atmosphere protection condition, wherein the protection gas is mixed gas of carbon dioxide and sulfur hexafluoride, and the proportion is 99:1. the smelting reduction temperature is 980 ℃, and the smelting time is 45min. In the smelting process, manual stirring is carried out for 3min at intervals of 5min.
(5) And (3) removing slag, cooling to 900 ℃, enabling the melt to enter a casting die of an electromagnetic vibration casting die system through a fine pore filter screen, keeping electromagnetic vibration when casting, and cooling to room temperature to obtain the magnesium-titanium intermediate alloy.
The contents of magnesium element and titanium element in the magnesium-titanium intermediate alloy obtained in the embodiment are shown in table 2, and the content of impurity element is Fe, cu, ni, si:0.061wt%.
Examples 8-10 were identical to the preparation of example 3, except that the raw material formulations were different, and the raw material formulations of examples 8-10 are shown in Table 1.
Comparative example 1
Comparative example 1 was identical to the preparation method of example 1, except that the raw material formulation was different, and specifically, the raw material formulation of comparative example 1 is shown in table 1.
Comparative example 2
Comparative example 2 is identical to the preparation method of example 1 except that the raw material formulation is different, and that in comparative example 2, alkali metal salt is not added but alkali earth metal salt is added, and the total mass of the alkali earth metal salt added in comparative example 2 is equal to the sum of alkali metal salt and alkali earth metal salt in example 1; the raw material formulation of comparative example 2 is shown in table 1.
TABLE 1
Wherein, each part of numerical values in table 1 refers to the mass part of numerical values of each raw material.
The following is a performance test.
In the same furnace, titanium particles are deposited in the cooling process of the same ingot, so that the same ingot has composition deviation in the same furnace. In order to detect the uniformity of the magnesium-titanium intermediate alloy, the same cast ingot discharged from the furnace in the same furnace number is selected to detect the titanium content and the impurity content. The ingot is divided into trisections according to thickness, and marked as upper part, middle part and lower part respectively, and is sampled and analyzed respectively, and the titanium content and the impurity content are detected by IPC.
Measurement of particle size of titanium particles in magnesium-titanium intermediate alloy is carried out according to the measurement of titanium particles in SEM pictures, sampling is carried out to obtain a position, which is 1/2 of the position, close to the edge of the ingot, of the middle part of the ingot, 2 pictures are tested, and as a result, the particle size of the titanium particles is averaged.
The results of the performance test of each example and comparative example are shown in table 2:
TABLE 2
As can be seen from the data of table 2, the titanium content in the magnesium-titanium master alloy obtained by the preparation method of the present application reaches about 5wt% to 35wt%, and the Ti deviation is less than ±5wt%; and the impurity content in the magnesium-titanium alloy is low. The average grain size of the titanium grains in the obtained magnesium-titanium intermediate alloy is smaller, and as can be seen from the surrounding tissue diagram of the titanium-magnesium intermediate alloy prepared in the example 2 shown in the attached figure 1, the grain size in the prepared magnesium-titanium intermediate alloy is more uniform, and the average grain size is about 3.2 mu m. The comparative example 1 was prepared in substantially the same manner as in example 1 except that the ratios of the raw materials were different, and the magnesium-titanium master alloy obtained in comparative example 1 had a titanium content of only 7.5% to 8.5%, whereas the magnesium-titanium master alloy obtained in example 1 had a titanium content of 12.9wt% to 14.8wt%, and it was found that the control of the ratios of the raw materials among magnesium ingots, titanium salts, alkali metal salts and alkaline earth metal salts had a technical effect of increasing the titanium content in the magnesium-titanium master alloy. Comparative example 2 when preparing magnesium-titanium master alloy, only alkaline earth metal salt was added without adding alkali metal salt, and the content of titanium particles in the obtained magnesium-titanium master alloy was relatively low.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. The scope of the invention is, therefore, indicated by the appended claims, and the description may be intended to interpret the contents of the claims.
Claims (10)
1. The preparation method of the magnesium-titanium intermediate alloy is characterized by comprising the following steps of:
mixing and smelting metal magnesium, titanium salt, alkali metal salt and alkaline earth metal salt, and forming; wherein the mass ratio of the metal magnesium to the titanium salt to the alkali metal salt to the alkaline earth metal salt is 1 (0.4-2.3): 0.5-2.6): 0-1.
2. The preparation method according to claim 1, wherein the titanium salt comprises potassium titanate, titanium chloride and titanium fluoride in a mass ratio of 1 (0-1): (0-1); and/or the number of the groups of groups,
the alkali metal salt comprises potassium salt and sodium salt with the mass ratio of (0.5-1.8) to (0-0.8); and/or the number of the groups of groups,
the alkaline earth metal salt is magnesium salt; and/or the number of the groups of groups,
the metal magnesium is magnesium ingot.
3. The method according to claim 2, wherein the potassium salt comprises potassium chloride and potassium fluoride in a mass ratio of (0.6-1): (0-1); and/or the number of the groups of groups,
the sodium salt is at least one of sodium chloride and sodium fluoride; and/or the number of the groups of groups,
the magnesium salt is at least one selected from magnesium chloride and magnesium fluoride.
4. The method according to claim 1, wherein the mass ratio of the magnesium ingot, the titanium salt, the alkali metal salt and the alkaline earth metal salt is 1 (1.4-2.3): 1.8-2.6): 0.3-0.75.
5. The method of any one of claims 1 to 3, wherein the smelting is performed under a protective atmosphere; the protective gas in the protective atmosphere is selected from two mixed gases of argon, carbon dioxide, sulfur hexafluoride, nitrogen and sulfur hexafluoride.
6. A method of preparation according to any one of claims 1 to 3, wherein the smelting is carried out with mechanical or manual stirring at a speed of 30r/min to 500r/min; or,
the smelting is carried out under electromagnetic stirring, the stirring power of the electromagnetic stirring is 30kW-100Kw, and the stirring frequency is 80Hz-800Hz.
7. A method of manufacture as claimed in any one of claims 1 to 3 wherein the shaping comprises casting and cooling shaping steps, the casting being carried out under electromagnetic vibration conditions, the electromagnetic vibration frequency being in the range 200Hz to 500Hz.
8. Magnesium-titanium intermediate alloy, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9.
9. The magnesium-titanium intermediate alloy according to claim 8, wherein the magnesium-titanium intermediate alloy comprises 65wt% to 95wt% of magnesium element and 5wt% to 35wt% of titanium element in terms of mass percent; and/or the average grain diameter of the titanium metal particles in the magnesium-titanium master alloy is 1-20 mu m.
10. A magnesium-titanium alloy, characterized in that the raw material for its preparation comprises the magnesium-titanium intermediate alloy according to any one of claims 8 to 9.
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