CN118957342A - A composite refining agent for casting aluminum alloy and preparation method thereof - Google Patents
A composite refining agent for casting aluminum alloy and preparation method thereof Download PDFInfo
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- CN118957342A CN118957342A CN202410995454.0A CN202410995454A CN118957342A CN 118957342 A CN118957342 A CN 118957342A CN 202410995454 A CN202410995454 A CN 202410995454A CN 118957342 A CN118957342 A CN 118957342A
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- 238000007670 refining Methods 0.000 title claims abstract description 146
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000005266 casting Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 112
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000011780 sodium chloride Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000004615 ingredient Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 239000011775 sodium fluoride Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 44
- 239000007788 liquid Substances 0.000 abstract description 39
- 239000002893 slag Substances 0.000 abstract description 28
- 238000007872 degassing Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 13
- 238000000926 separation method Methods 0.000 abstract description 9
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000000779 smoke Substances 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 12
- 229910052923 celestite Inorganic materials 0.000 description 12
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 230000005496 eutectics Effects 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 238000012795 verification Methods 0.000 description 6
- 229910010062 TiCl3 Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910004883 Na2SiF6 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/06—Obtaining aluminium refining
- C22B21/064—Obtaining aluminium refining using inert or reactive gases
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种铸造铝合金复合精炼剂及其制备方法，属于铸造铝合金精炼变质技术领域。其技术方案要点是：所述精炼剂由以下质量百分比的成分组成：NaCl 34‑36％，NaF 18‑22％，TiCl3 15‑17％，SrSO4 8‑12％，KPO3 9‑13％，Na2B4O7 6‑8％，制备方法包括配料、蒸发结晶、破碎和烘干脱水。本发明克服了传统精炼剂存在的除气除渣效率低、烟雾排放量大、渣铝分离效果差、功能单一等问题，精炼剂具有优异的除气除渣效果，可显著降低铸造铝合金液的气、渣含量，同时对铸造铝合金还有细化变质作用，可以消除气孔、夹杂物和粗大第二相对铸造铝合金力学性能的危害，提高铝合金的铸造流动性与力学性能。
The invention discloses a composite refining agent for cast aluminum alloy and a preparation method thereof, and belongs to the technical field of refining and modification of cast aluminum alloy. The key points of the technical scheme are: the refining agent is composed of the following components in mass percentage: NaCl 34-36%, NaF 18-22%, TiCl 3 15-17%, SrSO 4 8-12%, KPO 3 9-13%, Na 2 B 4 O 7 6-8%, and the preparation method includes batching, evaporation crystallization, crushing and drying and dehydration. The invention overcomes the problems of low degassing and slag removal efficiency, large smoke emission, poor slag-aluminum separation effect, and single function existing in traditional refining agents. The refining agent has excellent degassing and slag removal effect, can significantly reduce the gas and slag content of cast aluminum alloy liquid, and has a refining and modification effect on cast aluminum alloy, which can eliminate the harm of pores, inclusions and coarse second phase to the mechanical properties of cast aluminum alloy, and improve the casting fluidity and mechanical properties of aluminum alloy.
Description
Technical Field
The invention belongs to the technical field of cast aluminum alloy refining and modification, and particularly relates to a cast aluminum alloy composite refining agent and a preparation method thereof.
Background
The cast aluminum alloy is an aluminum alloy taking aluminum and silicon as main elements, has good casting performance, corrosion resistance and mechanical properties, and is widely used for casting and forming various aluminum alloy parts, such as engine cylinder bodies, cylinder covers, pistons, wheels and the like. The properties of cast aluminum alloys are closely related to their cleanliness. The pores and inclusions can fracture the cast aluminum alloy matrix, destroy the tissue continuity of the cast aluminum alloy, cause local stress concentration, become crack sources and crack propagation directions of the cast aluminum alloy fracture, and reduce the strength and plasticity of the cast aluminum alloy. The properties of cast aluminum alloys are also closely related to the morphology size of their α -Al grains, si phase and Fe-rich phase. Coarse alpha-Al grains, si phase and Fe-rich phase reduce the fluidity, strength and plasticity of the cast aluminum alloy, while fine and uniform alpha-Al grains, si phase and Fe-rich phase improve the fluidity, strength and plasticity of the cast aluminum alloy. Therefore, in the smelting process, the casting aluminum alloy liquid is required to be subjected to refining, degassing, deslagging, refining and modification treatment, so that the gas and slag content of the casting aluminum alloy is reduced, and the alpha-Al crystal grains, si phase and Fe-rich phase of the casting aluminum alloy are refined.
The invention patent of publication No. CN102286667A discloses a sodium-free refining agent for aluminum and aluminum alloy and a production method thereof, wherein the refining agent comprises the following components in percentage by mass: 15-25% of potassium fluoroaluminate, 5-15% of calcium fluoride, 10-25% of potassium carbonate, 10-25% of potassium sulfate, 5-15% of barium sulfate, 15-30% of potassium chloride and 3-5% of anhydrous aluminum chloride. The production method comprises the steps of raw material screening, proportioning, mixing, detecting and packaging.
The invention patent of publication No. CN86105179A discloses a modification refining agent of aluminum-silicon alloy, which comprises the following components in percentage by mass: 20-40% of NaCl, 40-60% of NaF, 5-15% of Na 3AlF65-15％,Na2SiF6 -30% of NaCl, 45-65% of NaF and 15-25% of Na 2SiF6. The modification refining agent consists of multiple Na salts, and has refining, purifying and refining modification effects.
The invention patent of publication No. CN85100320A discloses a long-acting flux for aluminum-silicon alloy, which is formed by mixing and pressing the following components in percentage by mass: 10-15% of SrCO 3, 6-10% of Mg powder, 2-5% of Sr (NO 2)28-12％,NaNO3 8-12％,K2CO3 -25%, 2-5% of carbon powder, 25-30% of refractory brick powder and 8-12% of catalyst.
From the results of literature data retrieval and production practice experience, existing cast aluminum alloy refining agents still have one or more of the following problems: (1) The degassing and deslagging efficiency of the refining agent is still low, and the production requirement of high-purity casting aluminum alloy is difficult to meet. (2) The function of the refining agent is single, and the production requirement of high-performance cast aluminum alloy is difficult to meet. (3) The emission of the irritating smog is large in the use process of the refining agent, the slag-aluminum separation effect is poor, and serious environmental pollution is caused. Therefore, the existing refining agent for casting aluminum alloy and the preparation method thereof still need to be improved and developed.
Disclosure of Invention
Aiming at the problems mentioned in the background art, the invention aims to provide a cast aluminum alloy composite refining agent and a preparation method thereof, which improve the degassing and deslagging efficiency of the refining agent, reduce the gas and slag content of cast aluminum alloy, refine and deteriorate alpha-Al crystal grains, si phase and Fe-rich phase, improve the cleanliness and mechanical property of cast aluminum alloy, reduce the emission of irritant smoke and aluminum slag and solve the problems in the background art by optimizing the component composition and the preparation method of the refining agent.
The technical scheme adopted by the invention for achieving the purpose is as follows:
The invention provides a cast aluminum alloy composite refining agent, which is characterized by comprising the following components in percentage by mass ：NaCl 34-36％,NaF 18-22％,TiCl315-17％,SrSO4 8-12％,KPO3 9-13％,Na2B4O7 6-8％.
NaCl is the main component of the composite refining agent, and reacts with aluminum liquid to generate AlCl 3,AlCl3 with the boiling point of 180 ℃ and has very high vapor pressure, the AlCl 3 is in a gaseous state in the aluminum liquid, and impurities and hydrogen in the aluminum liquid are adsorbed and captured in the floating process, and then the AlCl 3 and the hydrogen are discharged out of the aluminum liquid together, so that the slag removal and hydrogen removal effects are realized.
The main function of NaF is to adsorb and melt the impurities such as alumina, and the NaF molten salt can destroy the alumina film at first, melt the alumina, so that the impurities such as alumina are dissolved into the molten salt, and the slag removal function is achieved. Secondly, the interface wettability between the inclusions and the aluminum liquid can be reduced, the surface tension between the inclusions and the aluminum liquid can be improved, the separation of the inclusions such as alumina and the like and the aluminum liquid can be promoted, and the deslagging function of the composite refining agent can be enhanced.
Ti element generated by the reaction of TiCl 3 and aluminum liquid directly enters the aluminum liquid, plays a role in heterogeneous nucleation core structure in the solidification process of the aluminum alloy, refines alpha-Al grains of the aluminum alloy, enables the alpha-Al grains to be converted from coarse dendrites into nearly spherical or equiaxial shapes, and improves the fluidity, strength and plasticity of the cast aluminum alloy. AlCl 3 bubbles generated by the reaction can absorb and capture inclusions and hydrogen in the aluminum liquid in the floating process, so that the deslagging and hydrogen removing capacity of the composite refining agent is enhanced.
The Sr element generated by the reaction of SrSO 4 and the aluminum liquid enters the aluminum liquid to play a role in refining and modifying the eutectic Si phase, so that the eutectic Si phase is converted into fine particles or fibers from coarse needles, the harm of the coarse eutectic Si to the strength and the plasticity of the cast aluminum alloy is eliminated, and the strength and the plasticity of the cast aluminum alloy are improved. SO 2 bubbles obtained by the reaction can also adsorb and capture impurities and hydrogen in the aluminum liquid in the floating process, SO that the deslagging and hydrogen removing capacity of the composite refining agent is enhanced.
KPO 3 reacts with aluminum liquid to generate P element which enters the aluminum liquid, so that primary crystal Si phase in the cast aluminum alloy can be thinned. For hypereutectic cast aluminum alloys, the Si phase, in addition to forming the eutectic Si phase, also exists as a coarse bulk or lath-like primary Si phase. The P element can refine coarse primary crystal Si phase, so that the coarse block or lath primary crystal Si phase is converted into fine dispersed particles, the strength and plasticity of the cast aluminum alloy can be improved, and the wear resistance of the cast aluminum alloy can be enhanced.
The main function of Na 2B4O7 is to refine the Fe-rich phase in the modified cast aluminum alloy. Fe is an inevitable impurity element in cast aluminum alloys, and is usually present in the form of a coarse needle-like or flake-like Fe-rich phase such as Al 3Fe、FeSiAl3, which impairs the strength and plasticity of the cast aluminum alloys. Na 2B4O7 reacts with the aluminum liquid to generate B element, and the B element enters the aluminum liquid, so that coarse needle-shaped or flake-shaped Fe-rich phases can be converted into fine dispersed particles, the harm of the coarse Fe-rich phases to the strength and the plasticity of the cast aluminum alloy is eliminated, and the strength and the plasticity of the cast aluminum alloy are improved.
The invention provides a preparation method of a cast aluminum alloy composite refining agent, which is characterized by comprising the following steps in sequence:
step one: naCl, naF, tiCl 3、SrSO4、KPO3、Na2B4O7 is selected as a raw material for batching according to the component composition and the mass percentage of the composite refining agent;
Step two: adding ingredients into hot water, stirring and dissolving the ingredients into an aqueous solution, and then heating and evaporating the aqueous solution to obtain a solid crystal;
step three: crushing the solid crystals into particles with the particle size smaller than 2mm, and drying and dehydrating the particles to obtain the composite refining agent.
Preferably, the NaCl, naF, tiCl 3、SrSO4、KPO3、Na2B4O7 in step one has a purity of not less than 99.8%. The raw materials can be industrial products, industrial byproducts or naturally occurring minerals, but the purity of the raw materials is ensured, too many impurities cannot be contained, and the effect of the composite refining agent and secondary pollution to the cast aluminum alloy are influenced.
Preferably, in the second step, the temperature of the hot water is not lower than 50 ℃, the mass ratio of the hot water to the ingredients is 1-1.5, and the temperature of the aqueous solution during heating and evaporation is 100 ℃. Too little hot water or too low a temperature is difficult to stir ingredients to dissolve into an aqueous solution, while too much hot water can result in too long heating and evaporation times, increasing energy consumption and production costs.
Preferably, the temperature of the drying and dehydrating in the third step is 150-180 ℃, and the time of the drying and dehydrating is 3-5 hours. Too low a temperature or too short a time may result in incomplete dewatering. The temperature should not be too high, and the decomposition of the components would not be effective. Packaging and sealing treatment should be carried out as soon as possible after drying and dehydration so as not to cause moisture absorption.
The invention also provides a use method of the cast aluminum alloy composite refining agent, which is characterized in that the use amount of the composite refining agent is 0.1-0.2% of the weight of the cast aluminum alloy.
Compared with the prior art, the invention has the following beneficial effects:
(1) The composite refining agent has lower melting point and more excellent degassing and deslagging effects. The conventional preparation method of the existing refining agent is to mechanically crush chloride salt and fluoride salt and then directly mix the crushed chloride salt and fluoride salt to obtain the refining agent, the compositions are independent of each other, and the compositions lack synergistic effect during the refining agent, so that the refining agent has high melting point and low degassing and deslagging efficiency. The invention breaks through the tradition, adopts a solution evaporation method to prepare the composite refining agent, and through solution evaporation, the components are re-solidified and recrystallized to form eutectic with lower melting point, for example, the melting point of NaCl is usually 801 ℃, the melting point of NaF is usually 993 ℃, and after the NaCl and NaF eutectic are formed, the melting point is reduced to 698 ℃, so that the melting point of the composite refining agent is greatly reduced, the composite refining agent is easier to melt in the casting aluminum alloy liquid, and a more excellent degassing and deslagging effect is generated.
(2) The composite refining agent has the dual functions of refining and purifying and refining and modifying. The existing casting aluminum alloy refining agent generally only contains NaCl, KCl, naF, caF, C 2Cl6 and other components, and has the functions of degassing and deslagging, but lacks the function of refining and modifying the structure of the casting aluminum alloy. In order to refine and modify the cast aluminum alloy, a refining modifier must be added, so that not only the production cost but also the production procedures are increased. Besides the conventional NaCl and NaF, the composite refining agent also contains TiCl 3、SrSO4、KPO3、Na2B4O7, so that the components not only increase the degassing and deslagging functions of the composite refining agent, but also release trace Ti, sr, P, B elements into casting aluminum alloy liquid, and respectively refine and deteriorate alpha-Al crystal grains, eutectic Si phases, primary crystal Si phases and Fe-rich phases in the solidification process, so that the damage of coarse alpha-Al crystal grains, eutectic Si phases, primary crystal Si phases and Fe-rich phases to the mechanical properties of the casting aluminum alloy can be eliminated, and the strength and plasticity of the casting aluminum alloy can be improved.
(3) The composite refining agent is more environment-friendly and has lower production cost. The existing refining agent mainly uses NaCl, KCl, naF, caF, C 2Cl6 and other chlorine salt and fluorine salt as main components, and a large amount of irritating and unpleasant smog and corrosive gas can be generated in the use process, so that the environment is seriously polluted, and the health of workers is endangered. The existing refining agent has low degassing and deslagging efficiency, so that the consumption of the refining agent is increased to obtain a cleaner cast aluminum alloy, and the consumption of the refining agent is usually 0.3-0.5% of the weight of the cast aluminum alloy liquid. However, increasing the consumption of the refining agent increases the production cost, increases the discharge amount of aluminum slag, causes more serious environmental pollution, and simultaneously causes the content of alkali metal elements such as Na, ca, K and the like in the cast aluminum alloy to exceed the standard, thereby deteriorating the mechanical properties of the cast aluminum alloy. The composite refining agent reduces the content of fluoride and chloride, can reduce the emission of smoke, has higher degassing and deslagging efficiency, can reduce the consumption of the composite refining agent, can obtain high-clean cast aluminum alloy, can reduce the emission of aluminum slag, and can avoid the exceeding of the content of Na, ca, K and other alkali metals in the cast aluminum alloy, so that the use is more environment-friendly, the production cost is reduced, and the market competitiveness of cast aluminum alloy products is enhanced.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 shows the microstructure of a cast aluminum alloy ingot refined with the composite refining agent of example 1.
FIG. 2 is a microstructure of a cast aluminum alloy ingot refined using a commercially available conventional refining agent of comparative example 2.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the ：NaCl 35.12％,NaF19.84％,TiCl3 16.51％,SrSO4 10.06％,KPO3 11.45％,Na2B4O7 7.02％, composite refining agent for casting the aluminum alloy comprises the following components in percentage by mass: step one: naCl, naF, tiCl 3、SrSO4、KPO3、Na2B4O7 with the purity of 99.8 percent is selected as a raw material for proportioning according to the component composition and the mass percent of the composite refining agent; step two: adding the ingredients into hot water at 70 ℃ to be stirred and dissolved into an aqueous solution, wherein the mass ratio of the hot water to the ingredients is 1.2, and then heating the aqueous solution to 100 ℃ to evaporate to obtain a solid crystal; step three: crushing the solid crystal into particles with the particle size smaller than 2mm, and drying and dehydrating the particles at 160 ℃ for 4 hours to obtain the composite refining agent.
Example 2
The preparation method of the ：NaCl 34.03％,NaF21.96％,TiCl3 15.03％,SrSO4 11.79％,KPO3 9.22％,Na2B4O7 7.97％, composite refining agent for casting the aluminum alloy comprises the following components in percentage by mass: step one: naCl, naF, tiCl 3、SrSO4、KPO3、Na2B4O7 with the purity of 99.8 percent is selected as a raw material for proportioning according to the component composition and the mass percent of the composite refining agent; step two: adding the ingredients into hot water at 50 ℃ for stirring and dissolving into an aqueous solution, wherein the mass ratio of the hot water to the ingredients is 1.5, and then heating the aqueous solution to 100 ℃ for evaporation to obtain a solid crystal; step three: crushing the solid crystal into particles with the particle size smaller than 2mm, and drying and dehydrating the particles at 180 ℃ for 3 hours to obtain the composite refining agent.
Example 3
The preparation method of the ：NaCl 35.95％,NaF19.01％,TiCl3 16.97％,SrSO4 9.03％,KPO3 12.85％,Na2B4O7 6.19％, composite refining agent for casting the aluminum alloy comprises the following components in percentage by mass: step one: naCl, naF, tiCl 3、SrSO4、KPO3、Na2B4O7 with the purity of 99.8 percent is selected as a raw material for proportioning according to the component composition and the mass percent of the composite refining agent; step two: adding the ingredients into hot water at 90 ℃ to be stirred and dissolved into an aqueous solution, wherein the mass ratio of the hot water to the ingredients is 1, and then heating the aqueous solution to 100 ℃ to evaporate to obtain a solid crystal; step three: crushing the solid crystal into particles with the particle size smaller than 2 mm, and drying and dehydrating the particles at 150 ℃ for 5 hours to obtain the composite refining agent.
Comparative example 1
The preparation method of the ：NaCl 35.12％,NaF19.84％,TiCl3 16.51％,SrSO4 10.06％,KPO3 11.45％,Na2B4O7 7.02％, composite refining agent for casting the aluminum alloy comprises the following components in percentage by mass: step one: naCl, naF, tiCl 3、SrSO4、KPO3、Na2B4O7 with the purity of 99.8 percent is selected as a raw material for proportioning according to the component composition and the mass percent of the composite refining agent; step two: crushing the ingredients into particles with the particle size smaller than 2 mm, and drying and dehydrating the particles at 160 ℃ for 4 hours to obtain the composite refining agent.
Comparative example 2
The cast aluminum alloy refining agent sold in the market at present comprises the following components in percentage by mass: 36.13% of NaCl, 15.42% of KCl and 12.37% of CaF 2 16.84％,NaF 19.24％,C2Cl6, and the refining agent is obtained by directly crushing and mixing the raw materials after drying and dehydrating.
Verification example 1
Melting points of the composite refining agent of example 1, the composite refining agent of comparative example 1 and the refining agent of comparative example 2 were measured by an OXFORD-DSC500 type differential scanning calorimeter, respectively, and the results are shown in table 1. As can be seen from Table 1, the melting point of the composite refining agent of example 1 is obviously lower than that of the refining agents of comparative examples 1 and 2, which shows that the composite refining agent of the invention has lower melting point and is easier to be melted in casting aluminum alloy liquid, thereby not only being beneficial to reducing the refining temperature of the casting aluminum alloy liquid and reducing the oxidation burning loss of the aluminum liquid, but also being beneficial to exerting the degassing and deslagging functions of the composite refining agent and improving the degassing and deslagging efficiency.
Table 1 melting point of refining agent
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Melting Point/. Degree.C | 723 | 1280 | 1014 |
Verification example 2
The refining agents of examples 1-3 and comparative examples 1-2 were used for refining and modifying treatment of ADC12 cast aluminum alloy under the same conditions, the experimental furnace was a 20 ton regenerative gas aluminum melting furnace, the weight of cast aluminum alloy liquid was 20 ton, argon with purity of 99.9% was used as a carrier medium to blow the refining agent into the cast aluminum alloy liquid, the temperature of the cast aluminum alloy liquid during refining was 700 ℃, the refining time was 20 minutes, and the addition amount of the refining agent was 0.15% of the weight of the cast aluminum alloy liquid. And recording the use condition of the refining agent in the experimental process, including the combustion condition of the casting aluminum alloy liquid, the smoke emission condition, the smoke smell, the slag-aluminum separation condition and the aluminum slag viscosity condition, and finally collecting and weighing the aluminum slag, wherein the smaller the weight of the aluminum slag is, the better the slag-aluminum separation effect of the refining agent is represented, and the results are shown in Table 2. As can be seen from Table 2, the composite refining agents prepared in examples 1-3 have small discharge amount, small smoke irritation, slight aluminum water combustion during refining, easy slag-aluminum separation, loose aluminum slag and small aluminum slag amount. The composite refining agent of the comparative example 1 is obtained by directly crushing and mixing the materials without adopting a solution evaporation method, and has slightly poor slag-aluminum separation effect and slightly more aluminum slag quantity. The conventional refining agent used in comparative example 2 was found to be a commercially available refining agent, and the amount of smoke generated during refining was large, the burning of molten aluminum was severe, the separation of aluminum slag was difficult, the aluminum slag was viscous, and the amount of aluminum slag discharged was also large. Compared with the prior art, the composite refining agent is more environment-friendly in use, has easier slag-aluminum separation effect, and is beneficial to reducing the loss of aluminum and the discharge amount of aluminum slag.
Table 2 comparison of refining conditions of refining agent
Verification example 3
The hydrogen content and the slag content of the aluminum alloy liquid cast in the furnace before and after refining in example 2 were checked and tested on site by using an HDA-V hydrogen tester and an Analyze PoDFA slag tester, the hydrogen content and the slag content of the aluminum alloy liquid cast in the furnace before refining were subtracted from the hydrogen content and the slag content of the aluminum alloy liquid cast in the furnace after refining, and then divided by the hydrogen content and the slag content of the aluminum alloy liquid cast in the furnace before refining to obtain the degassing rate and the slag removal rate of the refining agent, respectively, and the results are shown in tables 3 and 4. As can be seen from tables 3 and 4, the degassing rate of the composite refining agent of examples 1-3 was 57% or more, the deslagging rate was 50% or more, while the degassing rate of the refining agent of comparative example 1 was 50.4%, the deslagging rate was 45.9%, the degassing rate of the commercial refining agent of comparative example 2 was only 47.8%, and the deslagging rate was only 41.2%, and it can be seen by comparison that the composite refining agent of the present invention has higher degassing deslagging efficiency.
TABLE 3 Hydrogen content of cast aluminum alloy liquid before and after refining and degassing ratio of refining agent
TABLE 4 slag content of cast aluminum alloy liquid before and after refining and slag removal rate of refining agent
Verification example 4
The microstructure of cast aluminum alloy ingots refined with the composite refining agent of example 1 and the commercial refining agent of comparative example 2 was examined, and the results are shown in fig. 1 and 2, respectively. As can be seen from FIG. 1, after refining by the composite refining agent of the invention, the grain structure of the cast aluminum alloy ingot is fine and uniform, and coarse dendritic alpha-Al grains, needle-shaped Si phase and Fe-rich phase are not found. As can be seen from FIG. 2, after refining with a commercially available conventional refining agent, the grain structure of the cast aluminum alloy ingot is coarse, the alpha-Al grains are in a coarse dendritic form, and the Si phase and the Fe-rich phase are in a coarse needle or lath form. As can be seen by comparison, the composite refining agent has obvious refining and modification effects on alpha-Al grains, si phases and Fe-rich phases of the cast aluminum alloy.
Verification example 5
The cast aluminum alloy liquid in the furnace after refining in verification example 2 was sampled and cast into cast aluminum alloy ingots, and the tensile mechanical properties of the cast aluminum alloy ingots were measured, and the results are shown in table 5. As can be seen from Table 5, the strength and plasticity of cast aluminum alloys are obviously higher than those of cast aluminum alloys refined by the refining agents of comparative examples 1 and 2 by refining the cast aluminum alloy liquid by the compound refining agents prepared in examples 1 to 3, which shows that the strength and plasticity of cast aluminum alloys can be obviously improved finally by refining the cast aluminum alloy liquid by the compound refining agents of the invention, and by greatly improving the cleanliness of cast aluminum alloys, refining coarse alpha-Al grains, si phases and Fe-rich phases.
TABLE 5 tensile mechanical Properties of cast aluminum alloys after refining
Claims (7)
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| CN115992313A (en) * | 2022-12-21 | 2023-04-21 | 广东领胜新材料科技有限公司 | Refining agent for electrical aluminum alloy liquid and preparation method thereof |
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