CN114703390B - A kind of refining agent and its combined on-line casting aluminum alloy refining and purification method with argon - Google Patents
A kind of refining agent and its combined on-line casting aluminum alloy refining and purification method with argon Download PDFInfo
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- 238000007670 refining Methods 0.000 title claims abstract description 92
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 76
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910052786 argon Inorganic materials 0.000 title claims abstract description 20
- 238000005266 casting Methods 0.000 title claims description 13
- 238000000746 purification Methods 0.000 title claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 44
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007789 gas Substances 0.000 claims abstract description 23
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- 238000007872 degassing Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 3
- 239000001257 hydrogen Substances 0.000 abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007664 blowing Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
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- 230000002829 reductive effect Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000956 alloy Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 239000002893 slag Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 238000003908 quality control method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
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- 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
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Description
技术领域technical field
本发明属于金属材料及冶金领域，更具体地，涉及一种精炼剂及其与氩气联合在线铸造铝合金精炼净化方法。The invention belongs to the field of metal materials and metallurgy, and more particularly relates to a refining agent and a method for refining and purifying an aluminum alloy combined with argon gas for on-line casting.
背景技术Background technique
在铝合金铸件中，材料的可靠性以及铸件的性能会因为夹杂物的存在面对极大的威胁。铝合金熔体中的夹杂物会导致氢难以除去，影响除气的效果。铝熔体中的夹杂物和氢之间存在相互作用，一般来说，铝液中氧化夹杂物越多，所吸附的氢也就越多，导致氢含量增加，促进了铸件中气孔的形成，影响着性能的高低。基体的连续性会被夹杂物的存在而破坏，提供疲劳裂纹萌生的核心，造成应力集中，促进裂纹扩展，使得零件的抗疲劳能力降低，伸长率和抗拉强度等零件的力学性能会严重被恶化，造成产品的早期失效。In aluminum alloy castings, the reliability of the material and the performance of the casting will be greatly threatened by the presence of inclusions. Inclusions in the aluminum alloy melt will make it difficult to remove hydrogen and affect the effect of degassing. There is an interaction between inclusions and hydrogen in the aluminum melt. Generally speaking, the more oxidized inclusions in the molten aluminum, the more hydrogen adsorbed, resulting in an increase in the hydrogen content and promoting the formation of pores in the casting. Affects the level of performance. The continuity of the matrix will be destroyed by the presence of inclusions, providing the core of fatigue crack initiation, causing stress concentration, promoting crack propagation, reducing the fatigue resistance of the parts, and the mechanical properties of the parts such as elongation and tensile strength will be serious. deteriorated, causing early failure of the product.
传统的铝合金制造过程中使用的精炼剂，会导致成品的导电性、导热性、耐腐蚀性不强，而且生产出来的合金铸件中的气孔度偏高，在铸件表面多会产生七孔，氧化杂物的比例也较高，影响了合金铸件的性能，在精炼的过程中的产物具有刺激性气味，对于工作人员人体危害极大。总而言之，精炼剂存在夹渣多、氧化烧损大、合金渣分离不彻底、除气除渣效果不佳的问题。The refining agent used in the traditional aluminum alloy manufacturing process will lead to poor electrical conductivity, thermal conductivity and corrosion resistance of the finished product, and the porosity in the produced alloy casting is high, and there will be seven holes on the surface of the casting. The proportion of oxidized impurities is also high, which affects the performance of alloy castings. The product during the refining process has a pungent odor, which is extremely harmful to the human body of the staff. All in all, the refining agent has the problems of more slag inclusion, large oxidation burning loss, incomplete separation of alloy slag, and poor degassing and slag removal effect.
另外铝合金熔体除气方式有炉内除气和在线除气，除气方法包括惰性气体除气和熔剂除气，前者利用高纯惰性气体氢分压扩散，实现除氢，后者利用熔剂与铝形成低沸点化合物挥发除氢。由于小气泡在上浮过程中一方面会吸附夹杂物，另一方面还会夹住氩气气泡和合金液接触面间的压力差，将溶于合金液中的氢吸入气泡内。惰性气体其虽然克服了活性气体腐蚀设备的缺点，但是其净化效率远远不如活性气体，更无法实现碱金属和碱土金属的去除。In addition, the degassing methods of aluminum alloy melt include furnace degassing and online degassing. The degassing methods include inert gas degassing and flux degassing. The former uses high-purity inert gas hydrogen partial pressure diffusion to achieve hydrogen removal, and the latter uses flux. It forms low-boiling compounds with aluminum to volatilize and remove hydrogen. Since the small bubbles will adsorb inclusions on the one hand during the floating process, on the other hand, they will also clamp the pressure difference between the argon gas bubbles and the contact surface of the alloy liquid, and absorb the hydrogen dissolved in the alloy liquid into the bubbles. Although inert gas overcomes the shortcomings of active gas corrosion equipment, its purification efficiency is far less than that of active gas, and it cannot achieve the removal of alkali metals and alkaline earth metals.
因此，要发挥材料的潜力，充分发挥自身性能，必须首先解决铸坯的生产和质量的控制。Therefore, in order to give full play to the potential of the material and give full play to its own performance, it is necessary to first solve the production and quality control of the casting billet.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术的不足，本发明提供了一种精炼剂及其制备方法、及使用该精炼剂与氩气联合在线铸造铝合金精炼净化方法，该精炼剂组成简单，通过设置精炼剂与氩气联合优化精炼净化工艺，获得晶粒细小、无夹渣、氢含量低的铝合金铸锭，且还能够显著的降低铝合金铸锭显微疏松尺寸，提高铸锭冶金质量，为后续研究开发出能新的、高性能的铝合金材料奠定良好的基础。In order to overcome the deficiencies of the prior art, the present invention provides a refining agent and a method for preparing the same, and a method for refining and purifying an aluminum alloy by using the refining agent and argon in combination with the online casting of aluminum alloys. Combined optimization of refining and purification process with gas can obtain aluminum alloy ingots with fine grains, no slag inclusion, and low hydrogen content, and can also significantly reduce the microscopic porosity of aluminum alloy ingots and improve the metallurgical quality of the ingots for subsequent research and development. The production of new, high-performance aluminum alloy materials has laid a good foundation.
本发明具体是通过如下技术方案实现的：The present invention is specifically realized through the following technical solutions:
本发明第一方面提供了一种精炼剂，所述精炼剂包括六氯乙烷、碳酸钠和氧化铝纳米颗粒。A first aspect of the present invention provides a refining agent comprising hexachloroethane, sodium carbonate and alumina nanoparticles.
根据本发明，所述精炼剂由六氯乙烷、碳酸钠和氧化铝纳米颗粒组成。According to the present invention, the refining agent consists of hexachloroethane, sodium carbonate and alumina nanoparticles.
根据本发明，所述氧化铝纳米颗粒的粒径为30~50nm，例如为30nm、40nm或50nm。According to the present invention, the particle size of the alumina nanoparticles is 30-50 nm, for example, 30 nm, 40 nm or 50 nm.
根据本发明，以精炼剂的总重量计，其中六氯乙烷35wt%~40wt%，碳酸钠20wt%~40wt%，氧化铝纳米颗粒20wt%~40wt%。According to the present invention, based on the total weight of the refining agent, 35wt% to 40wt% of hexachloroethane, 20wt% to 40wt% of sodium carbonate, and 20wt% to 40wt% of alumina nanoparticles.
优选地，以精炼剂的总重量计，其中六氯乙烷35wt%、36wt%、37wt%、38wt%、39wt%、40wt%；碳酸钠20wt%、22wt%、25wt%、28wt%、30wt%、32wt%、34wt%、35wt%、36wt%、38wt%、40wt%；氧化铝纳米颗粒20wt%、22wt%、25wt%、28wt%、30wt%、32wt%、34wt%、35wt%、36wt%、38wt%、40wt%。Preferably, based on the total weight of the refining agent, wherein hexachloroethane is 35wt%, 36wt%, 37wt%, 38wt%, 39wt%, 40wt%; sodium carbonate is 20wt%, 22wt%, 25wt%, 28wt%, 30wt% , 32wt%, 34wt%, 35wt%, 36wt%, 38wt%, 40wt%; alumina nanoparticles 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, 32wt%, 34wt%, 35wt%, 36wt%, 38wt%, 40wt%.
根据本发明，所述精炼剂的平均粒径为0.5mm~6mm。According to the present invention, the average particle size of the refining agent is 0.5 mm to 6 mm.
根据本发明，所述氧化铝纳米颗粒为α-Al2O3。相较于其他构型的氧化铝，研究发现，α-Al2O3纳米颗粒能够快速填充到熔体表面的保护膜缝隙中。According to the present invention, the alumina nanoparticles are α-Al 2 O 3 . Compared with other configurations of alumina, the study found that α-Al 2 O 3 nanoparticles can quickly fill into the gaps of the protective film on the melt surface.
本发明第二方面提供了上述的精炼剂的制备方法，该方法包括：A second aspect of the present invention provides a method for preparing the above-mentioned refining agent, the method comprising:
将碳酸钠与六氯乙烷、氧化铝纳米颗粒混合均匀后压实，然后经破碎处理得到所述精炼剂。The refining agent is obtained by mixing sodium carbonate, hexachloroethane and alumina nanoparticles uniformly, compacting, and then crushing.
根据本发明，所述精炼剂的粒径为0.5mm-6mm。According to the present invention, the particle size of the refining agent is 0.5mm-6mm.
本发明第三方面提供了使用上述精炼剂与氩气联合在线铸造铝合金精炼净化方法。A third aspect of the present invention provides a method for refining and purifying an aluminum alloy by using the above-mentioned refining agent in combination with argon gas.
根据本发明，所述方法包括如下步骤：According to the present invention, the method comprises the following steps:
（1）将铝合金锭放入经预热的铝合金熔炼炉中，进行熔炼；(1) Put the aluminum alloy ingot into the preheated aluminum alloy melting furnace for melting;
（2）当熔炼后的铝合金熔体导入静置炉并将其温度调整至730~740℃后，在搅拌条件下，通过导管将干燥的惰性气体和上述精炼剂喷入铝合金熔体进行炉内除气精炼；(2) When the smelted aluminum alloy melt is introduced into the static furnace and its temperature is adjusted to 730~740°C, under stirring conditions, dry inert gas and the above-mentioned refining agent are sprayed into the aluminum alloy melt through the pipe for furnace. Internal degassing and refining;
（3）使用陶瓷过滤板对步骤（2）的熔体进行过滤，即得所述铝合金。(3) Using a ceramic filter plate to filter the melt in step (2) to obtain the aluminum alloy.
根据本发明，步骤（1）中，所述铝合金没有特别的定义，例如为2000系铝合金或7000系铝合金。According to the present invention, in step (1), the aluminum alloy is not particularly defined, for example, it is a 2000 series aluminum alloy or a 7000 series aluminum alloy.
根据本发明，步骤（1）中，所述预热的温度为620~650℃，所述预热的时间为10~20min。According to the present invention, in step (1), the preheating temperature is 620-650° C., and the preheating time is 10-20 min.
根据本发明，步骤（2）中，所述搅拌的转速为20~40rpm，例如为20rpm、25rpm、30rpm、35rpm或40rpm。According to the present invention, in step (2), the rotational speed of the stirring is 20-40 rpm, for example, 20 rpm, 25 rpm, 30 rpm, 35 rpm or 40 rpm.
根据本发明，步骤（2）中，所述干燥的惰性气体为干燥高纯氩气，其纯度级别为99.999%。According to the present invention, in step (2), the dry inert gas is dry high-purity argon with a purity level of 99.999%.
根据本发明，步骤（2）中，所述精炼剂的添加量为1.5~3.0kg/t（熔体质量），例如为1.5kg/t、1.6kg/t、1.8kg/t、2kg/t、2.2kg/t、2.5kg/t、2.8kg/t、3kg/t。According to the present invention, in step (2), the added amount of the refining agent is 1.5~3.0kg/t (melt mass), such as 1.5kg/t, 1.6kg/t, 1.8kg/t, 2kg/t , 2.2kg/t, 2.5kg/t, 2.8kg/t, 3kg/t.
根据本发明，步骤（2）中，所述干燥的惰性气体的压力为0.20~0.60MPa，例如为0.20MPa、0.30MPa、0.40MPa、0.50MPa、0.60MPa，气体流量20~100L/min，例如为20L/min、30L/min、40L/min、50L/min、60L/min、70L/min、80L/min、90L/min、100L/min。According to the present invention, in step (2), the pressure of the dry inert gas is 0.20~0.60MPa, such as 0.20MPa, 0.30MPa, 0.40MPa, 0.50MPa, 0.60MPa, and the gas flow rate is 20~100L/min, such as 20L/min, 30L/min, 40L/min, 50L/min, 60L/min, 70L/min, 80L/min, 90L/min, 100L/min.
根据本发明，步骤（2）中，所述导管为设置多个开孔的导管。According to the present invention, in step (2), the conduit is a conduit provided with a plurality of openings.
根据本发明，步骤（2）中，所述导管的孔径为3~6mm，孔密度为1~5孔/cm2。According to the present invention, in step (2), the diameter of the conduit is 3-6 mm, and the hole density is 1-5 holes/cm 2 .
根据本发明，步骤（2）中，通过导管将干燥惰性气体和精炼剂喷入铝合金熔体后获得的气体气泡平均大小为0.5~20.0mm。According to the present invention, in step (2), the average size of gas bubbles obtained after spraying dry inert gas and refining agent into the aluminum alloy melt through a conduit is 0.5-20.0 mm.
根据本发明，步骤（2）中，除气的时间为30~90min。According to the present invention, in step (2), the time for degassing is 30-90 min.
根据本发明，步骤（3）中，所述过滤板的孔径为30~70目。According to the present invention, in step (3), the pore size of the filter plate is 30-70 meshes.
本发明的技术方案的有益效果如下：The beneficial effects of the technical scheme of the present invention are as follows:
根据保护膜强化理念，使用包括具有活性的氧化铝纳米颗粒、Na2CO3与六氯乙烷的精炼剂，其中氧化铝纳米颗粒很容易填充到熔体表面保护膜缝隙中，同时携带Na2CO3与六氯乙烷，在高温时分解产生COX与Cl2，润湿和部分溶解氧化物，增大铝合金熔体对氧化物的粘滞力，经由氩气吹送调整体系平衡状态，并与铝合金熔体中的H结合使得氢固定在氧化物中，由较小的颗粒聚集，形成较大的氧化夹杂，再经由过滤去除，从而降低铝合金熔体中氢含量。通过上述组分进行复配，并利用上述固氢作用与氧化夹杂的凝聚作用，充分结合除渣和除气，实现除气后的铝合金熔体中氢含量为0.01~0.06ml/100gAl，同时显著降低铝合金铸锭显微疏松尺寸。另外本发明通过选择精炼剂与高品位的氩气联合喷入与过滤净化的工艺，降低铸锭铝液的氢含量，可有利解决人工吹气不能完全达到气体分布均匀、更小的夹杂保留下来成为结晶核心使晶粒粗化等不利因素的影响，还能够大幅度减少气体用量。本发明精炼净化后得到的铝合金铸锭具有优异的冶金质量，无夹渣、氢含量低，还能够显著的降低铝合金铸锭显微疏松尺寸，提高铸锭冶金质量，为后续研究开发出能新的、高性能的铝合金材料奠定良好的基础。According to the protective film strengthening concept, a refining agent including active alumina nanoparticles, Na 2 CO 3 and hexachloroethane is used, wherein the alumina nanoparticles are easily filled into the gaps of the protective film on the melt surface and carry Na 2 CO 3 and hexachloroethane decompose at high temperature to generate CO X and Cl 2 , wetting and partially dissolving oxides, increasing the viscosity of aluminum alloy melt to oxides, adjusting the system equilibrium state by argon blowing, And combined with H in the aluminum alloy melt, the hydrogen is fixed in the oxide, and the smaller particles are aggregated to form larger oxide inclusions, which are then removed by filtration, thereby reducing the hydrogen content in the aluminum alloy melt. By compounding the above components, and using the above-mentioned solid hydrogen effect and the coagulation effect of oxidative inclusions, the slag removal and degassing are fully combined, so that the hydrogen content in the degassed aluminum alloy melt is 0.01~0.06ml/100gAl, and at the same time Significantly reduce the microporous size of aluminum alloy ingots. In addition, the present invention reduces the hydrogen content of the ingot aluminum liquid by selecting the refining agent and the high-grade argon gas combined injection and filtration purification process, which can advantageously solve the problem that artificial air blowing can not completely achieve uniform gas distribution, and smaller inclusions are retained. The influence of unfavorable factors such as becoming the crystal core and coarsening the crystal grains can also greatly reduce the amount of gas. The aluminum alloy ingot obtained after the refining and purification of the invention has excellent metallurgical quality, no slag inclusion and low hydrogen content, and can also significantly reduce the microscopic porosity of the aluminum alloy ingot, improve the metallurgical quality of the ingot, and develop an ingot for subsequent research. It can lay a good foundation for new, high-performance aluminum alloy materials.
具体实施方式Detailed ways
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following examples are only for illustrating and explaining the present invention, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the intended protection scope of the present invention.
下述实施例中所使用的实验方法如无特殊说明，均为常规方法；下述实施例中所用的试剂、材料等，如无特殊说明，均可从商业途径得到。The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
制备例1Preparation Example 1
选用99.999%品位的氩气。Use 99.999% argon gas.
制备例2Preparation Example 2
选用99.99%品位的氩气。Use 99.99% argon gas.
表1 制备例1和制备例2的氩气的组成Table 1 Composition of Argon in Preparation Example 1 and Preparation Example 2
实施例1Example 1
一种精炼剂，以该精炼剂的总重量计，其中六氯乙烷35%，碳酸钠35%，氧化铝纳米颗粒30%。所述精炼剂为平均粒径为3-6mm。A refining agent, based on the total weight of the refining agent, comprising 35% of hexachloroethane, 35% of sodium carbonate and 30% of alumina nanoparticles. The refining agent has an average particle size of 3-6mm.
所述的精炼剂的制备方法，该方法包括：将碳酸钠与六氯乙烷，氧化铝纳米颗粒固体粉末按上述用量混合均匀后压实，然后经破碎处理得到所述精炼剂A1。The preparation method of the refining agent includes: mixing sodium carbonate, hexachloroethane, and alumina nanoparticle solid powder according to the above-mentioned amounts, compacting, and then crushing to obtain the refining agent A1.
实施例2Example 2
一种精炼剂，以该精炼剂的总重量计，其中六氯乙烷40%，碳酸钠40%，氧化铝纳米颗粒20%。所述精炼剂为平均粒径为2-4mm。A refining agent, based on the total weight of the refining agent, comprising 40% of hexachloroethane, 40% of sodium carbonate and 20% of alumina nanoparticles. The refining agent has an average particle size of 2-4mm.
所述的精炼剂的制备方法，该方法包括：将碳酸钠与六氯乙烷，氧化铝纳米颗粒固体粉末按上述用量混合均匀后压实，然后经破碎处理得到所述精炼剂A2。The preparation method of the refining agent includes: mixing sodium carbonate, hexachloroethane, and alumina nanoparticle solid powder according to the above-mentioned amounts, compacting, and then crushing to obtain the refining agent A2.
实施例3Example 3
一种精炼剂，以该精炼剂的总重量计，其中六氯乙烷45%，碳酸钠45%，氧化铝纳米颗粒10%。所述精炼剂为平均粒径为3-6mm。A refining agent, based on the total weight of the refining agent, comprising 45% of hexachloroethane, 45% of sodium carbonate and 10% of alumina nanoparticles. The refining agent has an average particle size of 3-6mm.
所述的精炼剂的制备方法，该方法包括：将碳酸钠与六氯乙烷，氧化铝纳米颗粒固体粉末按上述用量混合均匀后压实，然后经破碎处理得到所述精炼剂A3。The preparation method of the refining agent includes: mixing sodium carbonate, hexachloroethane, and alumina nanoparticle solid powder according to the above-mentioned amounts, compacting, and then crushing to obtain the refining agent A3.
对比例1Comparative Example 1
一种精炼剂，以该精炼剂的总重量计，其中六氯乙烷45%，碳酸钠55%。所述精炼剂为平均粒径为3-6mm。A refining agent, based on the total weight of the refining agent, comprising 45% of hexachloroethane and 55% of sodium carbonate. The refining agent has an average particle size of 3-6mm.
所述的精炼剂的制备方法，该方法包括：将碳酸钠与六氯乙烷固体粉末按上述用量混合均匀后压实，然后经破碎处理得到所述精炼剂B1。The preparation method of the refining agent comprises: mixing sodium carbonate and hexachloroethane solid powder uniformly according to the above-mentioned dosage, compacting, and then crushing to obtain the refining agent B1.
测试例1Test Example 1
使用上述精炼剂与氩气联合在线铸造铝合金精炼净化方法，所述方法包括如下步骤：Using the above-mentioned refining agent and argon combined online casting aluminum alloy refining and purification method, the method comprises the following steps:
（1）将7000系铝合金锭放入经预热的铝合金熔炼炉中，预热温度650℃，预热时间20min。(1) Put the 7000 series aluminum alloy ingot into the preheated aluminum alloy melting furnace, the preheating temperature is 650℃, and the preheating time is 20min.
（2）当合金熔体导入静置炉并将其温度调整至740℃后，在搅拌条件下对熔体进行炉内除气精炼。其中炉内除气具体为采用导管将精炼剂和氩气喷入铝合金熔体进行除气，导管上设置有孔径为3~4mm的孔，孔密度为5孔/cm2；所述导管将精炼剂和氩气喷入铝合金熔体，控制气体压力为0.40MPa，气体流量80L/min，气泡平均大小为15~20.0mm，精炼剂的添加量为1.5kg/t，除气时间为60min；(2) After the alloy melt is introduced into the stationary furnace and its temperature is adjusted to 740°C, the melt is degassed and refined in the furnace under stirring conditions. Wherein, the degassing in the furnace is specifically to use a conduit to spray the refining agent and argon into the aluminum alloy melt for degassing, and the conduit is provided with a hole with a diameter of 3 to 4 mm, and the hole density is 5 holes/cm 2 ; Refining agent and argon are injected into the aluminum alloy melt, the gas pressure is controlled to be 0.40MPa, the gas flow rate is 80L/min, the average size of the bubbles is 15~20.0mm, the amount of refining agent added is 1.5kg/t, and the degassing time is 60min ;
（3）使用孔径为50目的陶瓷过滤板进行过滤，即得所述精炼铝合金。(3) Use a ceramic filter plate with a pore size of 50 meshes to filter to obtain the refined aluminum alloy.
分别将实施例1-2和对比例1-2制备得到的精炼剂、制备例1-2的氩气通过上述条件喷入，对精炼后的合金熔体进行直冷半连续浇铸，浇铸前在线测氢，测氧化夹杂含量。The refining agent prepared in Example 1-2 and Comparative Example 1-2, and the argon gas in Preparation Example 1-2 were injected through the above conditions, and the refined alloy melt was directly cooled and semi-continuously cast, and the casting was on-line. Measure hydrogen and measure the content of oxidized inclusions.
其中的在线液态含氢量是采用ABB在线测氢仪测试得到的，氧化夹杂除净率是采用统计方法测试得到的，具体为将精炼前和精炼过滤后所取样品进行显微组织观察制样，在200倍视野内随机选取20个位置进行观察计算，氧化夹杂除净率=（精炼前样品统计氧化夹渣数量-精炼后样品统计氧化夹渣数量）÷精炼前样品统计氧化夹渣数量×100%。具体测试结果详见表2。The online liquid hydrogen content is measured by ABB's online hydrogen measuring instrument, and the removal rate of oxidation inclusions is obtained by statistical methods. , randomly select 20 locations within a 200-fold field of view for observation and calculation, the removal rate of oxidation inclusions = (the number of oxidized slag inclusions in the samples before refining - the number of oxidized slag inclusions in the samples after refining) ÷ the number of oxidized slag inclusions in the samples before refining × 100%. The specific test results are shown in Table 2.
表2 精炼铝合金熔体及其铸造的铝合金铸锭的性能测试结果Table 2 The performance test results of the refined aluminum alloy melt and its cast aluminum alloy ingot
综上，使用包括具有活性的氧化铝纳米颗粒、Na2CO3与六氯乙烷的精炼剂与高品位的氩气联合喷入与过滤净化的工艺，降低铸锭铝液的氢含量，可有利解决人工吹气不能完全达到气体分布均匀、更小的夹杂保留下来成为结晶核心使晶粒粗化等不利因素的影响，还能够大幅度减少气体用量。本发明精炼净化后得到的铝合金具有稳定且较低的氢含量，从而能够显著的降低铝合金铸锭显微疏松尺寸，提高铸锭冶金质量，为后续研究开发出能新的、高性能的铝合金材料奠定良好的基础。To sum up, the use of the refining agent including active alumina nanoparticles, Na 2 CO 3 and hexachloroethane combined with high-grade argon injection and filtration purification technology can reduce the hydrogen content of ingot aluminum liquid, which can be It is beneficial to solve the influence of unfavorable factors such as artificial air blowing can not fully achieve uniform gas distribution, and smaller inclusions remain as crystallization cores to coarsen the grains, and can also greatly reduce the amount of gas. The aluminum alloy obtained after refining and purification of the invention has stable and low hydrogen content, so that the microscopic porosity size of the aluminum alloy ingot can be significantly reduced, the metallurgical quality of the ingot can be improved, and new and high-performance aluminum alloys can be developed for subsequent research. Aluminum alloy material lays a good foundation.
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The embodiments of the present invention have been described above. However, the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
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