WO2024072262A1 - Alliage d'aluminium de fonderie - Google Patents

Alliage d'aluminium de fonderie Download PDF

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Publication number
WO2024072262A1
WO2024072262A1 PCT/RU2023/050210 RU2023050210W WO2024072262A1 WO 2024072262 A1 WO2024072262 A1 WO 2024072262A1 RU 2023050210 W RU2023050210 W RU 2023050210W WO 2024072262 A1 WO2024072262 A1 WO 2024072262A1
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WIPO (PCT)
Prior art keywords
calcium
aluminum
zinc
magnesium
casting
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PCT/RU2023/050210
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English (en)
Russian (ru)
Inventor
Виктор Христьянович МАНН
Роман Олегович ВАХРОМОВ
Александр Юрьевич КРОХИН
Дмитрий Константинович РЯБОВ
Сергей Владимирович МАТВЕЕВ
Александр Николаевич АЛАБИН
Дмитрий Олегович Фокин
Original Assignee
Общество с ограниченной ответственностью "Институт легких материалов и технологий"
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Publication date
Priority claimed from RU2022125349A external-priority patent/RU2793657C1/ru
Application filed by Общество с ограниченной ответственностью "Институт легких материалов и технологий" filed Critical Общество с ограниченной ответственностью "Институт легких материалов и технологий"
Publication of WO2024072262A1 publication Critical patent/WO2024072262A1/fr

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    • 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
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon

Definitions

  • the invention relates to the field of metallurgy, namely to aluminum-based alloys, and can be used to produce castings of complex configurations by casting into a metal mold, mainly by injection molding.
  • castings of complex configuration are made from thermally non-hardening and hardenable alloys, mainly based on the Al-Si and Al-Mg systems.
  • Castings made from alloys based on the Al-Si system with additions of magnesium and/or copper, intended for the most critical parts, are usually used after heat treatment to states T7, Tb and T5 to increase strength properties.
  • thermally non-strengthening alloys based on the Al-Si system for example, A413.2 or alloys of the AlSill type
  • A413.2 or alloys of the AlSill type are characterized by high castability and good corrosion resistance.
  • the disadvantages of this group of alloys one should highlight the low level of strength characteristics, in particular, the yield strength usually in the cast state does not exceed 80 MPa.
  • a higher level of strength properties of castings in the cast state is ensured by the addition of copper; in particular, alloys of the A383.1 type or alloys of the AlSil2Cu2 type are known.
  • a significant decrease in corrosion resistance and a low level of relative elongation which usually does not exceed 1-2%, should be highlighted.
  • thermally non-hardening casting alloys based on the Al-Mg system for example, AMgbl, AMg5K, AMg5Mts (GOST 1583), Magsimal®59 (Rheinfelden Alloys), etc., characterized by satisfactory manufacturability during casting, good corrosion resistance, good level of strength properties and elongation.
  • high linear shrinkage and insufficient tightness of thin-walled castings should be highlighted.
  • the combination of a high level of strength properties, relative to elongation and corrosion resistance is realized in hardenable alloys of the Al-Si system with the addition of 0.2-0.5 wt.% magnesium, in particular, alloys such as AK9 (GOST 1583), Silafont®36 (Rheinfelden) Alloys), Trimal®37 (Trimet), etc.
  • Hardening significantly complicates the technological cycle for producing castings, since its use may cause warping of the castings (especially when using water quenching), changes in overall dimensions and the appearance of cracks.
  • a known casting alloy of the Al-Ni-Mn system is intended for the production of structural components for automotive and aerospace applications, which is an alternative to branded silumins, developed by Alcoa and disclosed in patent US 6783730 (published on August 31, 2004). From this alloy it is possible to obtain castings with a good combination of casting and mechanical properties with a content (wt.%) of 2-6 Ni, 1-3 MP, 1 Fe, less than 1 silicon, as well as containing other inevitable impurities.
  • a high level of casting and mechanical properties is ensured by the use of high purity grades of aluminum and a high nickel content, which significantly increases the cost of the resulting castings.
  • the proposed material is not thermally hardened over the entire concentration range, which limits its use, while in the region of high nickel concentrations the corrosion resistance of castings is significantly reduced.
  • a known material is based on the Al-Ni-Mn system, proposed by NUST MISIS and disclosed in patent RU 2478131 (published on March 27, 2013).
  • the material contains, wt.%: 1.5-2.5 Ni, 0.3-0.7 Fe, 1-2 p, 0.02-0.2 Zr, 0.02-0.12 Sc and 0.002- 0.1 Ce.
  • Castings obtained from the alloy after annealing are characterized by a tensile strength of at least 250 MPa with a relative elongation of at least 4%.
  • the first disadvantage of this alloy is its increased tendency to form concentrated porosity, which makes it difficult to obtain high-quality relatively large castings.
  • the second disadvantage is associated with the need to use elevated casting temperatures, which cannot always be realized in foundry conditions.
  • a material based on the A1-Ca system is known, proposed by NUST MISIS and disclosed in patent RU 2660492.
  • the material for use in the cast state contains, wt.%: 5.4-6.4 calcium, 0.3-0.6 silicon and 0.8-1.2 iron.
  • a material based on the A1-Ca system is known, proposed by NUST MISIS and disclosed in patent RU 2660492.
  • the material for use in the cast state contains, wt.%: 5.4-6.4 calcium, 0.3-0.6 silicon and 0.8-1.2 iron.
  • the disadvantages of the proposed alloy one should highlight the low relative elongation, which does not exceed 2.6%, which limits the use of the material in critical cast parts.
  • the closest to the proposed alloy is the invention of the Institute of Lightweight Materials and Technologies, disclosed in patent RU 2745595.
  • the material for use in the cast state contains, wt.%: 1.5-5.1 calcium, 0.1-1.8 zinc, up to 1.0 silicon and up to 0.7 iron.
  • the disadvantages of the proposed alloy one should highlight the low yield strength in the cast state, which is associated with low solubility alloying elements, with the exception of zinc, in solid solution and, as a result, insufficient solid solution strengthening.
  • the objective of the invention is to create a new cast aluminum alloy, intended for producing castings mainly by high-pressure casting, but not limited to, for use without heat treatment, characterized by good manufacturability during casting, a good level of mechanical characteristics, including a yield strength of at least 100 MPa , and high corrosion resistance.
  • the main application is casting for the automotive industry, housings for electronic devices, etc.
  • the material can be used to produce critical parts.
  • the technical result is the solution to the problem, ensuring high strength properties while maintaining ductility, manufacturability during casting and high corrosion resistance.
  • an aluminum-based casting alloy containing calcium, silicon, iron, zinc, magnesium and optionally (optional) at least one element from the group copper, manganese, chromium, titanium, zirconium, with the following concentrations of alloying elements, wt.%:
  • Silicon 0.05 - 0.8 (preferably 0.3 - 0.8)
  • Iron 0.05 - 1.0 (preferably 0.1 - 0.5)
  • Zinc 0.01 - 5.0 (preferably 1.0 - 2.0)
  • the alloy contains at least one alloying element from the group:
  • Manganese 0.01 - 1.5 (preferably 0.5 - 1.0) Chromium 0.01 - 0.2 (preferably 0.05 - 0.1)
  • Titanium 0.01 - 0.2 (preferably 0.05 - 0.1)
  • magnesium is located in an aluminum matrix, and copper is associated with calcium and forms a eutectic phase, which ensures an increase in strength properties without compromising ductility.
  • the alloy is used to produce castings that have the following tensile properties in the cast state: yield strength of at least 100 MPa.
  • Concentrations (wt.%) of calcium (2.0-5.2), silicon (0.05-0.8), iron (0.05-1.0), zinc (0.01-5.0) and copper (optionally 0.01-1.4) is limited to the stated limit, which ensures the formation of a structure consisting of an aluminum solution and corresponding eutectic phases containing calcium and the following elements: silicon, iron, zinc and, optionally, copper.
  • Calcium, silicon, iron, zinc and optionally copper influence the total amount of eutectic phase in the alloy.
  • the amount of eutectic with a minimum content (according to the stated range) of calcium, silicon, iron, zinc and optionally copper is about 2.5 vol.%.
  • the presence (wt.%) of magnesium (0.01-2.0) and, optionally, at least one element, including manganese (0.01-1.5), chromium (0.01-0.2), titanium (0.01-0.2) and zirconium (0.01-0.2) provide, in combination with the above elements (calcium, silicon, iron, zinc and, if available, copper) the formation of a structure that represents aluminum solution in the form of a primary crystallizing phase and eutectic, which contains at least one alloying element, including manganese, chromium, titanium and zirconium.
  • Magnesium and, optionally, at least one of the elements, including manganese, chromium, titanium and zirconium, to varying degrees, are capable of providing strengthening due to dissolution in an aluminum solid solution (solid solution strengthening), with magnesium and , optionally, at least one of the elements, including manganese, chromium, titanium and zirconium, within the stated limit increases the crystallization interval, which negatively affects casting characteristics.
  • Figure 1 shows a typical structure of the alloy in the cast state, which shows the primary aluminum solid solution and the eutectic phases.
  • the structure in the cast state of the material is represented by an aluminum solution that contains zinc, magnesium and eutectic phase particles containing compounds of aluminum, calcium with zinc, aluminum, calcium with iron and aluminum, calcium with silicon.
  • the structure in the cast state looks qualitatively similar and is represented by an aluminum solid solution containing zinc, magnesium manganese, chromium, titanium and zirconium, as well as particles of the eutectic phase containing compounds of aluminum, calcium with zinc, aluminum, calcium with iron, aluminum, calcium with silicon and aluminum, calcium with copper.
  • a calcium content of less than 2.0 wt.% will lead to a decrease in casting characteristics; the binding of elements such as silicon, iron, zinc and, optionally, copper to calcium will not be ensured.
  • a calcium content of more than 5.2 wt.% will lead to the formation of coarse inclusions of the primary phase of ACS, leading to a decrease in mechanical properties.
  • Silicon content in the range of 0.05-0.8 wt.% in combination with calcium ensures the achievement of a good level of elongation in the cast state due to the fact that silicon contributes to the dispersion of the eutectic.
  • silicon concentration is more than 0.8 wt.%, coarse intermetallic compounds containing silicon are formed in the structure and, as a result, reduce the mechanical properties.
  • Less than 0.05 wt.% silicon is no longer sufficient to form a eutectic with a favorable morphology, which leads to an insufficient level of elongation in the cast state.
  • Iron content in the range of 0.05-1.0 wt.% in combination with calcium provides improved casting characteristics with an acceptable level of elongation.
  • the iron content is less than 0.05 wt.%, the manufacturability of the alloy casting deteriorates, which manifests itself in the form of increased adhesion of the casting to the mold or mold.
  • the iron concentration is more than 1.0 wt.%, coarse intermetallic compounds of crystallization origin containing iron and calcium are formed in the structure, and, as a result, the mechanical properties are reduced.
  • Zinc content in the range of 0.01-5.0 wt.% helps to increase corrosion resistance and increase casting characteristics. When the zinc content is less than 0.01 wt.%, no positive effect of zinc on strength properties has been established. Starting from 0.01 wt.% it is noted modification effect, manifested in the form of a change in the morphology of the eutectic containing calcium. When the zinc concentration is more than 5.0 wt.%, coarse phases of crystallization origin containing zinc and calcium are formed, which negatively affects the mechanical properties of the alloy.
  • An (optional) copper content in the range of 0.01-1.4 wt.% helps to increase strength characteristics without compromising casting characteristics and maintaining corrosion resistance at an acceptable level. Maintaining satisfactory corrosion resistance with copper content is ensured by the binding of copper in phase with calcium.
  • the copper content is less than 0.01 wt.%, no positive effect of copper on mechanical and other properties has been established.
  • a modification effect is observed, manifested in the form of a change in the morphology of eutectic phases containing calcium due to the formation of phases containing copper and calcium.
  • the magnesium content in the range of 0.01-2.0 wt.% helps to increase the strength properties in the cast state.
  • the crystallization range significantly expands, which unacceptably worsens the casting characteristics, in particular, the hot brittleness index.
  • the magnesium content is less than 0.01 wt.%, the positive effect of magnesium on the strength properties in combination with other elements within the stated chemical composition has not been established.
  • Titanium in the range of 0.01-0.2 wt.% contributes to the modification of the primary precipitation of aluminum solid solution during crystallization. With a higher titanium content in the structure, primary crystals may appear, which will reduce the overall level of mechanical properties, and with a lower content, the positive effect of the influence of this element will not be realized.
  • the alloy may contain boron or carbon in quantities proportional to their content in the alloy. Boron and carbon, as independent elements, in relation to the range under consideration, do not have a significant effect on the mechanical and casting properties.
  • Zirconium in the range of 0.01-0.2 wt.% promotes solid solution strengthening in the cast state. Large quantities require the casting temperature to rise above typical levels, which reduces the durability of the casting molds and increases the tendency for hot cracks to form during casting.
  • the structure may contain a small amount of primary crystals in an amount of up to 0.3 vol.%, containing manganese and/or chromium, and/or zirconium, and/or titanium, to reduce the effect of the casting sticking to the walls of the mold.
  • Quantitative assessment of the phase composition was carried out in at least one of 2 ways: 1) by the calculation method using the Thermo-calc program; 2) metallographic method.
  • the crystallization interval was estimated in at least one of 2 ways: 1) calculated using the Thermo-calc program; 2) experimental in coordinates with the construction of a cooling curve in temperature-time coordinates, and the value of the crystallization interval as the difference between the liquidus temperature and the solidus temperature.
  • the alloys indicated in the examples were prepared and studied.
  • the alloys were prepared in an induction furnace or resistance furnace in graphite crucibles using primary aluminum with a content of at least 99.8 wt.% and 99.99 wt.% as a base, zinc with a content of at least 99.90 wt.%, copper with containing at least 99.9 wt.%, magnesium with a content of at least 99.9 wt.% (the purity of the starting metals used in the melt is indicated) and double alloys: AlCalO, AlFelO, AlMn20, AlSilO, AlT15, AlCrlO, AIZrlO. The sum of the remaining elements and inevitable impurities in the alloy did not exceed 0.05 wt.%, i.e. which are contained in primary aluminum and alloys, and which were not standardized during the preparation of the melt.
  • the crystallization of the alloys was carried out in a metal die - a “separately cast cylindrical sample” with a working part diameter of 10 mm and a mold temperature of up to 150 °C.
  • the casting properties of the alloys were assessed by the hot brittleness indicator using the “ring test”, where the best indicator is a ring with a minimum wall thickness with a constant outer diameter of 40 mm, crystallized without a crack in the row of 3, 7 and 10 mm.
  • Mechanical properties were assessed by uniaxial tension of separately cast samples in the as-cast state. Test speed 10 mm/mm, length of working part 50 mm in accordance with GOST 1583-93.
  • the “adhesion” criterion assessed the ability of the material to be separated from the surface of the metal mold without mechanical impact.
  • alloys were prepared in laboratory conditions according to the chemical composition in Table 1.
  • the results of determining the crystallization interval and analyzing the tendency to form hot cracks are given in Table 2.
  • the results of determining the mechanical properties are given in Table 3.
  • compositions 2-5 and 8-26 provide an acceptable level of resistance to the formation of hot cracks.
  • Compositions 1, 6, 7 are not applicable, since composition 1 is characterized by a high tendency to stick to the walls of the mold.
  • Composition 6 is characterized by a high tendency to form hot cracks, and composition 7 is characterized by an unsatisfactory structure containing unacceptable primary crystals containing calcium, iron, silicon and zinc, which significantly reduce the elongation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)

Abstract

L'invention se rapporte au domaine de la métallurgie, notamment à des alliages à base d'aluminium, et peut être utilisée lors de la production de coulages à parois fines et de forme complexe, notamment lors du coulage sous pression. Cet alliage de fonderie à base d'aluminium comprend, en % en poids: calcium: 2,0 – 5,2; silicium: 0,05 – 0,8; fer: 0,05 – 1,0; zinc: 0,01 – 5,0; magnésium: 0,01 – 2,0; éventuellement au moins un élément de dopage du groupe: cuivre: 0,01 – 1,4; manganèse: 0,01 – 1,5; chrome: 0,01 – 0,2; titane: 0,01 – 0,2; zirconium: 0,01 – 0,2; ainsi que de l'aluminium et des impuretés inévitables. Le résultat technique de la présente invention consiste en l'obtention de propriétés de résistance élevées tout en conservant la plasticité et l'aptitude à la production lors du coulage, ainsi qu'une résistance élevée à la corrosion.
PCT/RU2023/050210 2022-09-28 2023-09-07 Alliage d'aluminium de fonderie WO2024072262A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2022125349A RU2793657C1 (ru) 2022-09-28 Литейный алюминиевый сплав
RU2022125349 2022-09-28

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB539456A (en) * 1939-04-12 1941-09-11 Nat Smelting Co Improvements in or relating to aluminium base alloys
CA2485524C (fr) * 2002-06-24 2010-11-16 Corus Aluminium Walzprodukte Gmbh Procede de production d'un alliage al-zn-mg-cu a haute resistance
RU2714564C1 (ru) * 2019-08-15 2020-02-18 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Литейный алюминиевый сплав
RU2745595C1 (ru) * 2020-09-16 2021-03-29 Общество с ограниченной ответственностью "Институт легких материалов и технологий" Литейный алюминиевый сплав

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB539456A (en) * 1939-04-12 1941-09-11 Nat Smelting Co Improvements in or relating to aluminium base alloys
CA2485524C (fr) * 2002-06-24 2010-11-16 Corus Aluminium Walzprodukte Gmbh Procede de production d'un alliage al-zn-mg-cu a haute resistance
RU2714564C1 (ru) * 2019-08-15 2020-02-18 Общество с ограниченной ответственностью "Объединенная Компания РУСАЛ Инженерно-технологический центр" Литейный алюминиевый сплав
RU2745595C1 (ru) * 2020-09-16 2021-03-29 Общество с ограниченной ответственностью "Институт легких материалов и технологий" Литейный алюминиевый сплав

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