WO2011035652A1 - Matériau en alliage d'aluminium calorifuge haute résistance contenant du lithium et des terres rares, et son procédé de production - Google Patents

Matériau en alliage d'aluminium calorifuge haute résistance contenant du lithium et des terres rares, et son procédé de production Download PDF

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WO2011035652A1
WO2011035652A1 PCT/CN2010/075717 CN2010075717W WO2011035652A1 WO 2011035652 A1 WO2011035652 A1 WO 2011035652A1 CN 2010075717 W CN2010075717 W CN 2010075717W WO 2011035652 A1 WO2011035652 A1 WO 2011035652A1
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alloy
rare earth
aluminum alloy
strength
melt
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PCT/CN2010/075717
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Chinese (zh)
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门三泉
张中可
车云
陈新孟
李祥
胥光酉
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贵州华科铝材料工程技术研究有限公司
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Publication of WO2011035652A1 publication Critical patent/WO2011035652A1/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
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with copper as the next major constituent

Definitions

  • the invention relates to an aluminum alloy material and a preparation method thereof, in particular to an aluminum alloy material of a microalloying element and a rare earth element and a preparation method thereof.
  • Aluminum alloy is a younger metal material that was only used in industrial applications in the early 20th century.
  • Second World War aluminum was mainly used to make military aircraft.
  • the aluminum industry began to develop civilian aluminum alloys, expanding its application range from the aviation industry to the construction industry, container packaging, transportation, power and electronics industries.
  • Various sectors of the national economy, such as machinery manufacturing and petrochemicals, are applied to people's daily lives.
  • aluminum is used in a wide range and is second only to steel and is the second largest metal material.
  • high-strength aluminum alloy From the perspective of manufacturing and aluminum alloy products, it is customary to classify high-strength aluminum alloy into two types: deformed aluminum alloy and cast aluminum alloy; from the available temperature conditions, high-strength aluminum alloy is divided into ordinary aluminum alloy and high temperature ( Or heat resistant) aluminum alloy.
  • high-Cu-based aluminum alloys can be used to meet the needs of high temperature and high strength.
  • Al-Cu alloys include cast aluminum alloys and deformed aluminum alloys, and both cast and deformed belong to 2 series aluminum. Alloy; high-temperature high-strength aluminum alloy capable of satisfying both casting performance and easy deformation processing has not been reported publicly.
  • the cast aluminum alloy includes four series of AlSi system, AlCu system, AlMg system and AlZn system.
  • AlCu and AlZn aluminum alloys have the highest strength, but most of them are between 200Mpa and 300Mpa, and those with AlCu are higher than 400Mpa.
  • AlZn-based casting alloys have poor heat resistance. Therefore, compared with the deformed aluminum alloy, the cast aluminum alloy generally has a relatively limited application range due to its poor toughness. Many important applications, such as special heavy-duty truck wheels, aerospace aluminum alloys, etc., use deformed aluminum alloys instead of cast aluminum alloys.
  • the deformed aluminum alloy reduces defects by extrusion, rolling, forging, etc., refines the crystal grains, increases the density, and thus has high strength, excellent toughness, and good use performance.
  • the equipment and tooling molds have high requirements and many processes, so the deformed aluminum alloy has a long production cycle and high cost.
  • cast aluminum alloys have many advantages such as low cost, tissue isotropy, special organization, easy production of complex shapes, small batch production, and large batch production. Therefore, the development of a high-strength and tough-cast aluminum alloy material capable of replacing a partially deformed aluminum alloy and its casting forming process can achieve the purpose of casting forging, shortening the manufacturing cycle, and reducing the manufacturing cost, and has important theoretical significance and significant practical application. value.
  • the American Aluminum Association grades 201. 0 (1986) and 206. 0 (1967) were formed on the basis of the A-U5GT and have good mechanical properties and resistance to stress corrosion. However, since it contains 0.4% to 1.0% of silver, the material cost is high, and it is only used in military or other high-demand areas, which limits its application range.
  • ZL205A alloy has complex composition and contains seven alloying elements such as Cu, Mn, Zr, V, Cd, Ti and B.
  • ZL205A (T6) has a tensile strength of 510 MPa, which is the highest strength of cast aluminum alloys with registered grades.
  • ZL205A (T5) has the best toughness and an elongation of 13%.
  • the biggest drawback of ZL205A is its poor casting performance and high thermal cracking tendency. At the same time, due to its high formulation cost and small application range.
  • the above three types of high-strength and tough cast aluminum alloys belong to the Al-Cu system.
  • This series of alloys has high strength and good ductility and toughness.
  • the casting performance is poor, and the concrete performance is that the hot cracking tendency is large, the fluidity is poor, and the feeding is difficult.
  • this series of alloys have poor corrosion resistance and tend to intergranular corrosion.
  • the casting yield of this series of alloys is very low.
  • 2XXX deformed aluminum alloy brands At present, there are more than 70 2XXX deformed aluminum alloy brands officially registered, most of which are registered in the United States, of which only 2001, 2004, 2011, 2011A, 2111, 2219, 2319, 2419, 2519, 2021, 2A16, 2A17, 2A20 14 brands such as 2B16 are high-copper aluminum alloys with copper content above 5%, and only 4 grades of 2A16, 2A17, 2A20, 2B16 with copper content above 6%.
  • These deformed aluminum alloy formulations contain more Si, Mg, Zn and other components, and do not have elements such as rare earth (RE) which are microalloyed. Therefore, the formulation composition is far from the 2 series cast aluminum alloy, reflecting Different properties of the aluminum alloy with different production processes and deep processing.
  • RE rare earth
  • Superalloys also known as heat-resistant high-strength alloys, heat-strength alloys or superalloys, are an important metal material developed in the 1940s with the advent of aerospace turbine engines. They can withstand high temperature oxidizing atmospheres and gas corrosion conditions for a long time. Larger working loads, mainly used for hot end components of gas turbines, are important structural materials for the aerospace, marine, power generation, petrochemical and transportation industries. Some of these alloys can also be used in bioengineering for orthopedic and dental materials. Commonly used superalloys include nickel-based, iron-based, and cobalt-based alloys that can operate at temperatures ranging from 600 to 1100 °C; while heat-resistant aluminum alloys were developed during the Cold War.
  • the heat-resistant high-strength aluminum alloy is suitable for long-term large working load in a thermal environment below 400 °C, and is increasingly used in aerospace, heavy machinery and other fields.
  • the remaining high-temperature and high-pressure power components can be cast with heat-resistant high-strength aluminum alloy.
  • the heat-resistant high-strength aluminum alloy is divided into two major categories: alloy for casting and alloy for deformation.
  • heat-resistant high-strength alloys contain a variety of alloying elements, more than ten kinds.
  • the added elements act as solid solution strengthening, dispersion strengthening, grain boundary strengthening and surface stabilization in the alloy, so that the alloy can maintain high mechanical properties and environmental properties at high temperatures.
  • aluminum alloy materials used for casting high-temperature parts are only A201. 0, ZL206, ZL207, ZL208, 206. 0 in national standards, including aluminum-copper-manganese alloys and aluminum rare earth alloys; among them, aluminum-copper-manganese Most of the alloys are made of high-purity aluminum ingots, and the cost is high, while the aluminum rare earth alloys have relatively poor mechanical properties at room temperature.
  • high temperature and high strength aluminum alloys generally have low temperature strength (the instantaneous tensile strength above 250 °C is less than 200 MPa, and the permanent strength is less than
  • the strength is mostly less than 100 Mpa at temperatures above 250 °C, and the main alloying elements except Cu, Mn
  • the heat-resistant high-strength aluminum alloy materials with Si, Mg, and Zn as main microalloying elements without adding these elements and having a strength of 150 Mpa or more at temperatures above 250 °C have not been reported.
  • the technical problem to be solved by the invention is that the melt treatment process existing in the field of high-strength aluminum alloy is extensive, the quality is poor, the hot cracking tendency is large, the casting performance is poor, the product yield is low, the high temperature strength is low, the waste material and the slag material are returned.
  • Technical problems such as poor use, guided by high-quality melt, solid solution and phase diagram theory, reduce the alloy quasi-solid phase temperature range by optimizing the alloy main elements Cu, Mn and rare earth elements, and solve the problem of high thermal cracking tendency and high temperature of products during casting.
  • Low-strength including instantaneous strength and long-lasting strength
  • preferred low-cost multi-microalloying element formulation creating material basis conditions for the cultivation and fine crystallization of high-temperature and strengthening phases in solid solution
  • the smelting and heat treatment process technology can fully realize the sufficient cultivation and fine crystallization of the high temperature phase and the strengthening phase in the solid solution.
  • a new type of high-strength heat-resistant (casting and deforming) aluminum alloy material of rare earth multi-component micro-alloyed AlCu was developed.
  • Cd 0. 01 ⁇ 0 ⁇ 5%
  • Ti the composition of the alloy is Cu: 1. 0 ⁇ 10. 0%, Mn: 0. 05 ⁇ 1.
  • Cd 0. 01 ⁇ 0 ⁇ 5%
  • Ti 0. 01 ⁇ 0 ⁇ 5%
  • ⁇ 0 ⁇ 01 ⁇ 0 ⁇ 2%
  • Zr 0 ⁇ 01 ⁇ 1 ⁇ 0%
  • Li 0. 1 ⁇ 3 ⁇ 0%
  • RE 0. 05 ⁇ 5 %
  • the rest is Al.
  • the above rare earth element RE is a single rare earth element or one or more mixed rare earth elements.
  • the above rare earth element RE includes La, Ce, Pr, Nd, Er, ⁇ .
  • the preparation method of the novel high-strength heat-resistant aluminum alloy comprises the following steps:
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component.
  • Powder metallurgy products include manganese, copper, zirconium, lithium, boron or titanium metal powder mixed with flux; flux refers to a mixture of alkali metal or alkaline earth metal halide salts (such as NaCl, KC1, N3 ⁇ 4A1F 6, etc.)
  • melt refining should be carried out in a closed environment as much as possible.
  • the present invention has the following main advantages:
  • Al-Cu high strength and toughness aluminum alloy (ZL201A, ZL 204A, ZL 205A, etc.) Most of them use refined aluminum as the base material and add more than one thousandth of precious elements. The cost is high, resulting in high strength and tough aluminum of Al-Cu system. Alloys can only be used in cutting-edge fields such as aerospace and defense military. The civilian sector is limited in application due to low cost performance.
  • the invention develops a new high-strength heat-resistant aluminum alloy material by adopting the general aluminum raw material, without adding (or adding less) precious elements, preferably the characteristic micro-alloying element formula, and adopting intensive, concise melting casting and purification processes. Overcoming the cost threshold of existing materials.
  • the present invention has the following eight advantages.
  • the dual attributes of the material From the point of view of the material use properties, it belongs to the amphoteric aluminum alloy. It has the characteristics of cast aluminum alloy and the characteristics of deformed aluminum alloy. It can be directly used to cast various light and powerful functional parts and structural parts, or it can be cast into rods first. The material is then hot extruded into profiles of various sections.
  • the material belongs to a multi-microalloyed cast aluminum alloy, but due to its excellent fluidity and intergranular self-lubricating properties, it has the easy processing characteristics of the deformed aluminum alloy.
  • the melted alloy liquid absorbs a large amount of gas in the air, moisture, etc. when melted and smelted in an open or poorly sealed furnace, resulting in insolubility.
  • Ordinary large-scale industrial aluminum alloy melting furnace is a reflective heating furnace or holding furnace that uses liquid or gaseous fuel as energy source. It requires a large amount of air to assist combustion, and the combustion products contain a large amount of water vapor and C0 2 , ! ( etc.
  • the lower electrode is easily chemically reacted with aluminum to form various harmful impurities. At the same time, these impurities are as easily adsorbed as the aluminum liquid, causing the melt to be seriously contaminated.
  • the melt Before casting, the melt must undergo one or several special purifications. After the process, and after passing the sampling test, the casting process can be entered, which undoubtedly prolongs the operation process, and the energy consumption and pollution indicators are difficult to reduce.
  • the equipment must be enlarged, the investment increased, and the technology is improved. Access thresholds; and the cost of overhaul and startup costs of equipment have doubled with the size and long process of equipment.
  • the preparation method required by the invention adopts an induction electric heating device with a sealing cover to eliminate the contamination of the melt by air, water vapor and various combustion products during fuel combustion, and at the same time, protection can be adopted during the melting process.
  • the gas is smelted in a protective atmosphere to maximize the insulation of the air; since the high purity of the melt is maintained, a simple pass-through degassing and slag removal device can be adopted in the subsequent casting stage without having to add a special stay. Insulation purification equipment, which greatly simplifies the process.
  • the application number is 200810302670. 3, 200810302668. 6, 200810302669. 0 and 200810302671.
  • the four patent names are all "a high-strength cast aluminum alloy material".
  • the heat treatment process parameters of the specified material are "620 °C”. In the following, within 72 hours, in the material application test, it was found that when the temperature at the solution treatment exceeds 560 °C, the phenomenon of "overburning" often occurs, causing damage to the microstructure of the material, which is typically characterized by strength and ductility. The main indicators are significantly reduced, the castings become brittle, the surface is dark and dark, and even cracks, deformations and scraps occur during heat treatment.
  • the heat treatment process parameters are optimally adjusted to: 470 to 560 ° C, solution treatment within 30 hours.
  • the base alloy of the new material series can be made of ordinary industrial pure aluminum (ie double zero aluminum, Including aluminum liquid and aluminum ingot for remelting), it has to adopt the formula of refined aluminum or high-purity aluminum as the base alloy than the existing high-strength aluminum alloy, which has the advantages of sufficient raw material supply, low cost and convenient procurement;
  • the material can also be made of fine aluminum or high-purity grade aluminum as the base alloy, and the material of this formulation is more ductile than the general-purpose aluminum-based material.
  • the invention creates a material basis for the cultivation and fine crystallization of the high temperature phase and the strengthening phase in the solid solution by using the alloying elements copper (Cu), manganese (Mn) and a multi-alloyed composition characterized by lithium (Li). Under the condition that the main element Cu and Mn form a strengthened ⁇ phase (Al 2 Cu) and a T phase (Al 12 Mn 2 Cu), high-temperature element lithium (Li) and RE are selected as complex alloying trace addition elements.
  • Li forms five kinds of dispersive high-temperature strengthening phases such as Al 2 Li 3 and AlLi 5 in the alloy, and rare earth (RE) forms a diffused high-temperature strengthening phase of various metal compounds in the alloy (for example: rare earth Ce forms a -C in the alloy) ⁇ Alu e -C ⁇ Al and other 7 kinds of metal compounds; rare earth La forms 6 kinds of metal compounds such as a -AlnLas P AlnLas in the alloy; rare earth Pr forms a -Al u Pr 3 ⁇ ⁇ _Al u Pr 3 in the alloy 6 Metal compound; rare earth Nd forms 6 kinds of metal compounds such as ⁇ - Al u Nd 3 ⁇ ⁇ - Al n Nd 3 in the alloy; rare earth Er forms ErAl 3 , ErAl 2 , ErAl , Er 3 Al 2 , Er 2 in the alloy 5 kinds of metal compounds such as Al; rare earth Y forms A1 3 Y, A1 2 Y, A1Y, A
  • the mechanism of action of the main alloying elements of the present invention is as follows.
  • the material allows the copper (Cu) content to be in the range of 1 to 10%, which is slightly different from the range of 3 to 11% of the Cu-containing (Cu) in the Al-Cu-based cast aluminum alloy, but is theoretically extremely significant.
  • Alternative meaning is slightly different from the range of 3 to 11% of the Cu-containing (Cu) in the Al-Cu-based cast aluminum alloy, but is theoretically extremely significant.
  • the copper (Cu) content is 5.65 ⁇ 5. 7%, it is exactly equal to the eutectic solubility of Cu in the Al-Cu alloy, and in the heat treatment process, according to "complete solid solution-uniform precipitation-grain boundary strengthening" change (bonding, mosaic, slip) "mode and the shift mechanism with a grain gap filler, forming Cu-rich more strengthening phase (i.e., including the Al 2 Cu phase 5), so that the aluminum alloy
  • the mechanical properties at room temperature and high temperature are greatly improved, and the processing performance is also improved.
  • the solubility of Cu in A1 decreases sharply with the decrease of temperature. During the process of crystal solidification, the supersaturation of Cu in ⁇ -A1 solid solution increases rapidly.
  • Precipitation at the grain boundary and dissolution into the crystal form more defects between the grain boundaries, lowering the room temperature and high temperature strength of the alloy, so the Cu content is too low, which is meaningless for a simple Al-Cu alloy; If more rare earth elements (RE) are added to the alloy, it can serve to compensate for the special effect of the low Cu content.
  • RE rare earth elements
  • the Cu-rich phase cannot be completely absorbed by the matrix during heat treatment, and is dispersed in the grain boundary in the form of a boundary-rich Cu metal compound, which lowers the concentration difference of Cu-sites in the solid solution of ⁇ -A1 in vivo and in vivo.
  • the strength of the Cu-rich phase discharged from the ⁇ -A1 solid solution dendrites to the grain boundary is moderated, that is, the structural stress and thermal cracking tendency are lowered.
  • the Cu content is 5.7%
  • the more Cu-rich phase the smaller the structural stress and thermal cracking tendency inside the alloy during crystallization; meanwhile, the Cu-rich phase with high melting point fine crystal dispersion forms active heterogeneity during melt crystallization.
  • the crystal nucleus accelerates the melt crystallization reaction but prevents the crystal nucleus from growing, refines the crystal grains, and also reduces the thermal cracking tendency of the alloy; and makes the filling between the grain boundaries of the substrate more full; the Cu-rich phase can also interact with Al, Various elements such as Mn form a refractory metal compound. All of these effects significantly weaken the surface tension of the melt and lower the melt viscosity, thereby significantly improving melt flow and casting properties of the alloy.
  • the Cu content in the alloy should be 11 ⁇ 12%.
  • the excessive Cu phase has a preferential network property to form a huge network structure, and the viscosity of the alloy is greatly enhanced.
  • the excess phase replaces the aluminum matrix in the crystallization process to become a main factor for controlling crystallization.
  • the excellent effects of the original dispersion on the aluminum matrix phase are all shielded, so the various properties of the alloy are greatly reduced.
  • the reasonable range of determining the Cu content of the main alloying elements is: l ⁇ 10% (wt%). 2
  • This material improves the corrosion resistance with manganese (Mn) element while shielding the impurity Fe to reduce the harmful effects of Fe.
  • rare earth RE as the basic micro-alloying element, and its content range is large, up to 5%, which can fully exert the degassing, slag removal, purification, fine grain and metamorphism of rare earth elements in the alloy, Improve the mechanical properties and corrosion resistance of the alloy.
  • Rare earth elements are highly active, have strong affinity for oxygen, hydrogen, sulfur, nitrogen, etc., and their deoxidation ability exceeds the most powerful deoxidizer aluminum available.
  • the content of oxygen is 50 * 10-6, 10-6 * 10 off to the following, which can effect the desulfurization of the S content to 20 ⁇ 5 * 10-6 * 10-6 off. Therefore, the rare earth-containing aluminum alloy is easily chemically reacted with the above substances in the aluminum liquid during smelting, and the reaction product is insoluble in aluminum and enters the slag, thereby lowering the gas content in the alloy, causing pores and shrinkage in the alloy product. The tendency is greatly reduced.
  • Rare earth elements can significantly improve the mechanical properties of the alloy.
  • the rare earth element can form a stable high melting point intermetallic compound such as A1 4 RE, Al 8 CuRE, Al 8 Mn 4 RE, Al 24 RE 3 Mn or the like in the aluminum alloy.
  • These high-melting-point intermetallic compounds are dispersed in the inter-crystal and dendrites in the form of a network or a skeleton, and are firmly bonded to the matrix to strengthen and stabilize the grain boundaries.
  • a certain amount of AlSiRE phase is formed in the alloy. Because of its high melting point and hardness, it has a good effect on improving the heat resistance and wear resistance of the alloy.
  • the low-melting impurity elements Sn, Pb, Sb, etc. in the molten metal can be neutralized, and they form a compound having a high melting point or uniformly distribute them from the dendrite to the entire crystal, thereby eliminating the dendrite structure.
  • Rare earth elements have fine grain and metamorphism.
  • Rare earth elements are surface active elements, which can be concentrated at the crystal interface, reduce the melt viscosity, enhance the fluidity, and reduce the tensile force between the phases, because the work of forming the critical size nucleus is reduced, and the number of crystal nuclei is increased. Refine the grain.
  • the metamorphism of rare earth on aluminum alloy has long-lasting effect and remelting stability. Most of the single or mixed rare earths have strong refinement and metamorphism on the ⁇ -A1 phase.
  • the rare earth element can also improve the electrical conductivity of the alloy. Since the rare earth can refine the aluminum crystal grains, it can also form stable compounds (such as CeFe 5 , CeSi, CeSi 2 , etc.) in the alloy, such as CeFe 5 , CeSi , CeSi 2 , etc., and precipitate out from the crystal, together with the purification effect of the rare earth on the alloy, The electrical resistivity of aluminum is lowered and the electrical conductivity is improved (about 2%).
  • the rare earth addition amount of aluminum alloy is generally less than 1%, in 200810302670. 3, 200810302668. 6, 200810302669. 0 and 200810302671. 3% ⁇
  • the application of the rare earth content is determined to be 0. 05 ⁇ 0. 3%. From the phase diagram of the A1-RE alloy, since most of the rare earths have a low solubility in aluminum (e.g., Ce is about 0.01%), the presence of the high-melting intermetallic compound is mostly distributed in the grain boundary or the inside of the crystal. Due to its high activity, it acts as a purifying agent in the purification of the melt.
  • Lithium (Li) element is a characteristic additive element for complex alloying.
  • Five kinds of metal compounds such as Al 2 Li 3 and AlLi 5 can be formed in the alloy, and the dispersed phase is distributed in the grain boundary of the matrix to improve the room temperature and high temperature strength of the alloy.
  • ZL208, 206. 0 and other high-strength cast aluminum alloys solve the major problems of high thermal cracking tendency and low casting pass rate of the above-mentioned aluminum alloy casting; old material remelting and new materials can realize any proportion of ingredients, new and old materials mixed
  • the melt casting performance is unchanged, and it has a good effect of stabilizing the strength of the material and improving the ductility.
  • the recyclability is poor and the circulation route is long, which is extremely economical and intensive.
  • the principle of eliminating the hot cracking tendency of new materials is as follows:
  • the Cu-rich phase is formed due to the increase of copper content in the alloy, and the Cu-rich phase is dispersed as a high-melting-point fine-grained phase in the form of a metal compound, which effectively offsets the crystal during melt crystallization.
  • the Cu-rich solute in the granule has a strong tendency to diffuse to the grain boundary due to the sharp increase in supersaturation, thereby slowing down the structural stress during crystallization.
  • the Cu-rich phase and the Li rare earth microalloying element and Mn are at the grain boundary.
  • Various dispersion phases of Zr, Ti, B and other elements have various functions of refining crystal grains, filling matrix grain boundaries, and forming near-aluminum potential metal compounds, all of which significantly weaken the surface tension of the melt and reduce The melt viscosity, which significantly improves the melt flowability and the casting properties of the alloy, ensures a high yield of the cast product.
  • the multi-microalloying effect has long-lasting property and remelting stability.
  • the structural characteristics of the melt maintain the atomic group structure and fineness formed by the primary alloy melt.
  • Crystal structure a large number of active crystal nuclei can fully play the role of agglomeration and assimilation of microcrystalline structure in the melt, and can maintain the original fluidity. Therefore, the blending of the old materials has a good effect of stabilizing the strength of the material and improving the ductility.
  • This property of the old material can be completely reused at the production site. Whether it is slag, machining residue or unqualified casting, it can be smelted together with the new material or directly added to the melt.
  • the characteristics of the present invention are significantly improved compared with the currently widely used 1XXX series and 2XXX series high-strength aluminum alloy materials, and the amount of waste products is greatly reduced, so that no large waste yard is required at the production site (in actual production)
  • Aluminum alloy foundry often has to plan a large waste dumping site.
  • many cast aluminum alloys do not have remelting stability and cannot be reused directly on site. Therefore, batch batch processing is required for centralized manufacturing. Cost, a series of processing links and invalid labor are derived; and all the additional links, costs and ineffective labor can be omitted by applying the new materials provided by the present invention.
  • the material has the characteristics of high-temperature aluminum alloy, which can reach a strength of more than 200Mpa at 400 °C, higher than the traditional high-temperature (heat-resistant) aluminum alloy material, which makes the new material can replace the aerodynamic engine body directly.
  • Heat-resistant parts of materials other than high-temperature gas-burning parts. See Characteristics 4 "Scientific and Economical Formulations" in the contents of copper-rich phase, rare earth (RE), and heat-resistant alloy element Li).
  • Table 1 lists the elemental compositions of the 31 aluminum alloys which are similar in performance and use in one aspect of the invention. It can be seen that the present invention has the following innovations in comparison with existing various high copper content deformed aluminum alloys, heat resistant deformed aluminum alloys, and heat resistant cast aluminum alloys.
  • the copper (Cu) content is allowed to be large in the range of 1 to 10%; at the same time, manganese (Mn) elements are combined to form various high-temperature strengthening phases.
  • the second is to use rare earth (RE) as the basic micro-alloying element, and its content range is large, up to 5%, which can fully exert the degassing, slag removal, purification and fine graining of rare earth (RE) in the alloy.
  • RE rare earth
  • the rare earth (RE) is a surface active element which can be concentratedly distributed at the crystal interface to reduce the tensile force between the phase and the phase, because the work for forming the critical size crystal nucleus is reduced, and the number of crystal nuclei is increased, thereby refining the crystal grains.
  • the low melting point elements such as magnesium and zinc are not used as the material for producing the strengthening phase, and the decomposition and conversion of the reinforcing phase of the material at high temperature are avoided, thereby significantly increasing the high temperature strength of the material.
  • the fifth is lithium (Li) element as a characteristic additive element of complex alloying.
  • Five kinds of metal compounds such as Al 2 Li 3 and AlLi 5 can be formed in the alloy, and the dispersed phase is distributed in the matrix grain boundary in the melt to improve the alloy. Room temperature and high temperature strength.
  • the combination of titanium (Ti), boron (B) and zirconium (Zr) elements as a comprehensive grain refiner gives the alloy material a material basis for all excellent properties such as high strength, high toughness, heat resistance and high fluidity.
  • High copper content deformed aluminum alloy, heat resistant deformation aluminum alloy, heat resistant cast aluminum alloy and the composition of the present invention 1. High copper content deformed aluminum alloy Order number /
  • the Applicant compares the present invention with the mechanical properties of several existing high strength and toughness aluminum alloys, as shown in Table 2.
  • the data listed in 1 is a high purity 206.0 alloy, ie W (Si) 0.05%, W (Fe) 10%.
  • the tensile strength of the present invention is 480 to 540 MPa, and the hardness is greater than that of HB140, which is obviously superior to the mechanical properties of the existing high-strength and tough aluminum alloy.
  • the room temperature strength of the present invention is greater than 450 MPa
  • the high temperature strength is above 300 MPa at 250 ° C
  • the high temperature strength is greater than 200 MPa at a high temperature strength of 300 ° C, which is significantly better than the high temperature of the existing heat resistant high strength alloy. Persistence.
  • the novel high-strength heat-resistant aluminum alloy material of the invention has high-tech content, wide application fields and excellent market prospects, and its excellent cost performance makes it possible to replace almost all high-strength aluminum alloys and high-temperature aluminum alloys. , representing the development direction of light and strong structural materials in China and the world. detailed description
  • Example 1 Cu-1. 0%, characteristic microalloying element _Li, basic microalloyed rare earth element -La
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component, which comprises a mixture of manganese, copper, zirconium, lithium, boron or titanium metal powder and a flux.
  • Flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1, and N3 ⁇ 4A1F 6.
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.) ), and stir evenly, and to prevent the melt from inhaling moisture and burning, the melt refining should be operated in a closed environment as much as possible.
  • a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 2 Cu-4. 2%, characteristic microalloying element -Li, basic microalloyed rare earth element _La, Ce mixed rare earth
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component, which comprises a mixture of manganese, copper, zirconium, lithium, boron or titanium metal powder and a flux.
  • Flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1, and N3 ⁇ 4A1F 6.
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.) ), and stir evenly, and to prevent the melt from inhaling moisture and burning, the melt refining should be operated in a closed environment as much as possible.
  • a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.)
  • the melt refining should be operated in a closed environment as much as possible.
  • the alloy liquid is poured out of the furnace, and the gas is degassed and slag removed online.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 3 Cu-6. 01%, characteristic microalloying element _Li, basic microalloyed rare earth element _La, Ce, Pr mixed rare earth
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component, which comprises a mixture of manganese, copper, zirconium, lithium, boron or titanium metal powder and a flux.
  • Flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1, and N3 ⁇ 4A1F 6.
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.) ), and stir evenly, and to prevent the melt from inhaling moisture and burning, the melt refining should be operated in a closed environment as much as possible.
  • a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 4 Cu-8%, characteristic microalloying element -Li, basic microalloyed rare earth element -Nd
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component, which comprises a mixture of manganese, copper, zirconium, lithium, boron or titanium metal powder and a flux.
  • Flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1, and N3 ⁇ 4A1F 6.
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.) ), and stir evenly, and to prevent the melt from inhaling moisture and burning, the melt refining should be operated in a closed environment as much as possible.
  • a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 5 Cu-7%, characteristic microalloying element _Li, basic microalloying rare earth element _Er
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component, which comprises a mixture of manganese, copper, zirconium, lithium, boron or titanium metal powder and a flux.
  • Flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1, and N3 ⁇ 4A1F 6.
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.) ), and stir evenly, and to prevent the melt from inhaling moisture and burning, the melt refining should be operated in a closed environment as much as possible.
  • a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 6 Cu-10. 0%, characteristic microalloying element _Li, basic microalloyed rare earth element -Y
  • the mixed metal additive refers to a cake-like or massive non-sintered powder metallurgy product for adding and adjusting an alloy component, which comprises a mixture of manganese, copper, zirconium, lithium, boron or titanium metal powder and a flux.
  • Flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1, and N3 ⁇ 4A1F 6.
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.) ), and stir evenly, and to prevent the melt from inhaling moisture and burning, the melt refining should be operated in a closed environment as much as possible.
  • a refining agent is added to the alloy melt (chlorine, hexachloroethane, manganese chloride, etc. may be used as a refining agent according to different working conditions, and a boron salt modifier, etc.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Physics & Mathematics (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

Cette invention concerne un matériau en alliage d'aluminium calorifuge haute résistance, constitué (en % poids) de : Cu 1,0 à 10,0%, Mn 0,05 à 1,5%, Cd 0,01 à 0,5%, Ti 0,01 à 0,5%, B 0,01 à 0,2%, Zr 0,01 à 1,0%, Li 0,01 à 1,0%, terre rare 0,05 à 5%, le reste étant de l'Al. L'alliage peut résoudre les problèmes de forte tendance à la fissuration thermique lors du coulage et de faible résistance du produit aux hautes températures. Cette invention concerne en outre le procédé de production du matériau en alliage d'aluminium.
PCT/CN2010/075717 2009-09-23 2010-08-05 Matériau en alliage d'aluminium calorifuge haute résistance contenant du lithium et des terres rares, et son procédé de production WO2011035652A1 (fr)

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CN102828088A (zh) * 2011-06-14 2012-12-19 湖南晟通科技集团有限公司 一种Cu-Mn高强度耐热铝合金材料

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