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WO2011035653A1 - Co-RE高强耐热铝合金材料及其制备方法 - Google Patents

Co-RE高强耐热铝合金材料及其制备方法 Download PDF

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Publication number
WO2011035653A1
WO2011035653A1 PCT/CN2010/075718 CN2010075718W WO2011035653A1 WO 2011035653 A1 WO2011035653 A1 WO 2011035653A1 CN 2010075718 W CN2010075718 W CN 2010075718W WO 2011035653 A1 WO2011035653 A1 WO 2011035653A1
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alloy
rare earth
aluminum alloy
melt
strength
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PCT/CN2010/075718
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English (en)
French (fr)
Inventor
张中可
车云
陈新孟
门三泉
胥光酉
李祥
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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 WO2011035653A1 publication Critical patent/WO2011035653A1/zh

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0408Light metal alloys
    • C22C1/0416Aluminium-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/12Alloys based on aluminium with copper as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057Changing 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 300Mp a , and only AlCu is 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 alloy instead of cast aluminum alloy.
  • the deformed aluminum alloy reduces defects by extrusion, rolling, forging, etc., refines the crystal grains, improves 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 price, tissue isotropy, special organization, easy production of complex shapes, small batch production, and mass 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 areas where defects are required, 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.
  • the series of alloys are high in strength and good in plasticity and enthalpy.
  • 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.
  • High-strength cast aluminum alloy material consisting of Mn, Ti, Cr, Cd, Zr, B and rare earth elements. This aluminum alloy material has high tensile strength and elongation, and tensile strength reaches 44 (pa, elongation). More than 6%; but such high-strength cast aluminum alloy materials still fail to solve the problem of large thermal cracking tendency during use, and the contradiction between alloy strength and castability is prominent.
  • the main reason is the composition of Cu and Mn in the main elements of the alloy.
  • the range of alloy quasi-solid phase temperature is wide. It provides sufficient conditions for anisotropic dendrite development during casting solidification, and forms strong internal shrinkage stress in the late solidification stage. Therefore, the shrinkage hot cracking tendency is large.
  • 2XXX deformed aluminum alloy grades there are more than 70 2XXX deformed aluminum alloy grades 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
  • High-temperature alloys also known as heat-resistant high-strength alloys, heat-strength alloys or super-alloys
  • high-temperature alloys also known as heat-resistant high-strength alloys, heat-strength alloys or super-alloys
  • 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, which can work in 600 ⁇ 110 (TC high temperature environment; while heat-resistant aluminum alloys are developed during the Cold War.
  • Heat-resistant high-strength aluminum alloys are suitable for 400 ° In the thermal environment below C, it has been subjected to large working loads for a long time, and has been used more and more in aerospace and heavy machinery. In addition to components such as aero-turbine engines and gas turbines that directly contact high-temperature gas, the rest of the high-temperature and high-pressure Strong power components can be cast in 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 A20 L 0, ZL206, ZL207, ZL208,
  • the current heat-resistant high-strength aluminum alloy generally has low temperature strength (the instantaneous tensile strength above 250 °C is less than 200Mpa, the permanent strength is less than 100Mpa), the formula cost is high, the casting performance is poor, the casting pass rate is low, the waste material and the slag material are returned.
  • the strength is mostly less than 100 Mpa at temperatures above 250 °C, and the main alloying elements except Cu, Mn
  • 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 a temperature of 250 ° C or higher 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 serviceability, guided by high-quality melt, solid solution and phase diagram theory, reduce the quasi-solid phase temperature range of the alloy by optimizing the alloy main elements Cu, ⁇ 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.
  • 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 material 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, cobalt, boron or titanium metal powder mixed with flux; flux refers to a mixture of alkali metal or alkaline earth metal halogen salts (such as NaCl, KC1, Na 3 AlF 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
  • ZL20 LA, 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 toughness of Al-Cu system.
  • Aluminum alloys can only be used in cutting-edge fields such as aerospace and defense military, and 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.
  • melt uptake is an important measure to maintain melt quality and casting quality.
  • 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 , ( ⁇ and other substances, at high temperatures.
  • 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.
  • 200810302670. 3, 200810302668. 6, 200810302669. 0 and 200810302671. 8 are all in the invention of "a high-strength cast aluminum alloy material", and the heat treatment process parameters of the specified materials are "620 ⁇ or less”.
  • the temperature of the solution treatment exceeds 560 , it was found that when the temperature of the solution treatment exceeds 560 , the phenomenon of "over-burning" often occurs, resulting in the destruction of the microstructure of the material.
  • the typical characteristics are the main indicators such as strength and ductility. Lowering, the casting becomes brittle, the surface is dark and dark, and even cracks and deformations occur during heat treatment and are scrapped.
  • 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-aluminum, including aluminum and remelting aluminum ingots), which must be made of refined aluminum or high-purity aluminum than the existing high-strength aluminum alloy.
  • Formula for base alloy The model has the advantages of sufficient raw material supply, low cost and convenient procurement.
  • the material can also be made of refined aluminum or high-purity grade aluminum as the base alloy, and the material of this formula is higher than the general-purpose material of the variety. Extensibility.
  • 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 the preferred alloying elements copper (Cu), manganese (Mn) and multi-alloyed alloys characterized by cobalt (Co).
  • copper copper
  • Mn manganese
  • Co multi-alloyed alloys characterized by cobalt (Co).
  • the main element Cu, Mn forms strengthened e Al 2 Cu
  • T phase Al 12 Mn 2 Cu
  • high temperature element cobalt (Co) and RE are selected as complex alloying trace addition elements
  • Co AlCo formed in the alloy 190) 8 kinds of phase 2 and the like diffuse high temperature strengthening
  • Co trace additive element is complicated alloyed high-strength aluminum alloy casting.
  • a complex strengthening phase such as Al 4 (NiCoFeMn) is formed between the dendrites, which hinders dislocations and prevents grain slippage, and effectively increases the room temperature and high temperature (at 40 CTC) of the alloy.
  • Rare earth (RE) forms a diffuse high-temperature strengthening phase of various metal compounds in the alloy (for example: rare earth Ce forms 7 kinds of metal compounds such as ⁇ - Ce 3 Al u ⁇ ⁇ - Ce 3 Al in the alloy; rare earth La forms in the alloy 6 kinds of metal compounds such as ⁇ -A1 U L3 ⁇ 4 ⁇ 1 U L; rare earth Pr forms 6 kinds of metal compounds such as ⁇ -Al encounterPr 3 ⁇ f3—Al u Pr 3 in the alloy; rare earth Nd forms a _Al u in the alloy 6 kinds of metal compounds such as Nd 3 ⁇ e _ Al uNd 3 ; rare earth Er forms five metal compounds such as ErAl 3 , ErAl 2 , ErAl, Er 3 Al 2 and Er 2 Al in the alloy; rare earth Y forms A1 3 in the alloy Y, A1 2 Y, Al Y , Al 2 ⁇ 3, ⁇ 1 5 kinds of metal compound; Dy, 3 ⁇ P- DyAl 3 is formed of six kinds of metal
  • the rare earth Tm forms three kinds of refractory active metal compounds such as Al 3 Tm and AlTm in the alloy; the rare earth Yb forms two kinds of refractory active metal compounds such as Al 3 Yb and Al 2 Yb in the alloy; and the rare earth Lu forms Al 3 in the alloy. Lu, 11 ⁇ 2 and other five refractory active metal compounds, etc.) all increase the room temperature strength, heat resistance and melt flowability of the alloy.
  • 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" Phase-gap filler (bonded, inlaid, non-slip)
  • the transformation mode and mechanism of action change, forming more Cu-rich strengthening phase (including Al 2 Cu or 3 phase), which greatly improves the room temperature and high temperature mechanical properties of the aluminum alloy, and also improves the processing performance;
  • the solubility in A1 decreases sharply with the decrease of temperature.
  • the strengthening phase is insufficient, and the transformation mode and mechanism of the strengthening phase are difficult to fully exert.
  • 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 (E) are added to the alloy, it can serve to compensate for the special effect of the Cu content being too low.
  • the Cu-rich phase cannot be completely absorbed by the matrix during heat treatment, and is dispersed in the grain boundary at the boundary of the Cu-rich metal compound, which reduces the Cu-site in the solid solution of ⁇ -A1 in vivo and in vivo.
  • the difference in concentration, during the solidification process smoothes the strength of the Cu-rich phase of the ⁇ -A1 solid solution dendrites to the grain boundary, which reduces the structural stress and thermal cracking tendency.
  • 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, reducing the harmful effect 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 R 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 modification effect 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 ⁇ 1 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%.
  • a phase analysis of the A1-RE alloy of A because most of the rare earths have a very low solubility in aluminum (such as Ce is about 0.01%), and the presence of high-melting intermetallic compounds is distributed in the grain boundary or the interior of the base crystal. .
  • the copper content and the rare earth content is considered to determine the content range of 0. 05 ⁇ 5%.
  • 4Cobalt (Co) element is a characteristic addition element of complex alloying.
  • 8 kinds of metal compounds such as AlCo and 1 9 (3 ⁇ 4) can be formed, and the dispersed phase is distributed in the grain boundary of the matrix, and the room temperature and high temperature strength of the bismuth alloy are obtained.
  • Casting performance is higher than current A201. 0, ZL206, ZL207, ZL208, 206 . 0 high-strength cast aluminum alloy, which solves the major problems of high thermal cracking tendency and low casting pass rate when casting aluminum alloy; old material remelting and new material can realize any proportion of ingredients, new and old material mixed melt pouring
  • the performance is unchanged, and it has the 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 Co-rare-earth microalloying element and Mn are on 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 more than 200Mpa under 40CTC conditions, higher than the traditional high-temperature (heat-resistant) aluminum alloy material. This feature makes the new material can replace the high-temperature gas directly in addition to the aircraft engine body. Heat-resistant parts of materials other than the burnt parts. (See the characteristics of heat resistance principle 4
  • 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 mainly has the following innovations as compared with 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 the addition of cobalt (Co) element as a characteristic alloying element.
  • Co cobalt
  • eight kinds of metal compounds such as AlCo and human 1 ⁇ 02 can be formed, 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.
  • 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 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 30 (at TC, the high temperature durability is greater than 200 MPa, 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 -Co, 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, cobalt, boron or titanium metal powder and a flux.
  • the flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1 and Na 3 AlF 6 .
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 2 Cu-4. 2%, characteristic microalloying element -Co, basic microalloying 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, cobalt, 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.
  • melt refining agent 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.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 3 Cu-6. 01%, characteristic microalloying element -Co, 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, cobalt, boron or titanium metal powder and a flux.
  • the flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1 and Na 3 AlF 6 .
  • the above alloy melt is subjected to in-furnace refining; a refining agent is added to the alloy melt (chlorine gas, 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 gas, 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.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 4 Cu-8%, characteristic microalloying element -Co, basic microalloying 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, cobalt, boron or titanium metal powder and a flux.
  • the flux refers to a mixture of alkali metal or alkaline earth metal halide salts, including NaCl, KC1 and Na 3 AlF 6 .
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 5 Cu-7%, characteristic microalloying element -Co, basic microalloyed 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, cobalt, 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.
  • melt refining agent 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.
  • the casting is subjected to a solution treatment at 470 to 560 ° C for 30 hours.
  • Example 6 Cu-10. 0%, characteristic microalloying element -Co, 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, cobalt, 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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Description

Co-RE高强耐热铝合金材料及其制备方法 技术领域
本发明涉及一种铝合金材料及其制备方法, 特别涉及一种微合金化元素及稀土元素的铝 合金材料及其制备方法。 背景技术
铝合金是一种较年轻的金属材料, 在 20世纪初才开始工业应用。 第二次世界大战期间, 铝材主要用于制造军用飞机。 战后, 由于军事工业对铝材的需求量骤减, 铝工业界便着手开 发民用铝合金, 使其应用范围由航空工业扩展到建筑业、 容器包装业、 交通运输业、 电力和 电子工业、 机械制造业和石油化工等国民经济各部门, 应用到人们的日常生活当中。 现在, 铝材的用量之多, 范围之广, 仅次于钢铁, 成为第二大金属材料。
从制造业和铝合金制品的角度, 习惯上把高强度铝合金分为变形铝合金和铸造铝合金两 类; 从制品可用的温度条件划分, 高强度铝合金又分为普通铝合金和高温 (或耐热)铝合金。 到目前为止, 能够满足高温高强需要的, 只有 Al-Cu系铝合金, 从牌号系列上讲, Al-Cu系合 金包括铸造铝合金和变形铝合金, 而不论铸造还是变形, 都属于 2系铝合金; 而能够同时满足 铸造性能好又容易进行变形加工的高温高强度铝合金, 还没有见公开报道过。
1、 高强度铸造铝合金和变形铝合金
一般铸造铝合金包括 AlSi系、 AlCu系、 AlMg系和 AlZn系 4个系列, 其中以 AlCu系和 AlZn 系铝合金的强度最高, 但多数在 200Mpa〜300Mpa之间, 高于 400Mpa的只有 AlCu系的少数几个 牌号, 但因采用精铝基体且加入贵重元素, 制造成本很高; AlZn系铸造合金的耐热性能很差。 因此, 一般铸造铝合金与变形铝合金相比因强韧性稍逊使其应用范围受到较大的限制。 许多 重要用途如特种重载车负重轮、 航空用铝合金等多采用变形铝合金, 而不是铸造铝合金。 变 形铝合金通过挤压、 轧制、 锻造等手段减少了缺陷, 细化了晶粒, 提高了致密度, 因而具有 很高的强度、 优良的韧性以及良好的使用性能。 但是, 对设备和工装模具要求高, 工序多, 因此变形铝合金生产周期长、 成本很高。 与变形铝合金相比, 铸造铝合金具有价格低廉、 组 织各向同性、 可以获得特殊的组织、 易于生产形状复杂的零件、 可以小批量生产也可以大批 量生产等诸多优点。 因此, 开发出能够替代部分变形铝合金的高强韧铸造铝合金材料及其铸 造成形工艺, 可以达到以铸代锻、 缩短制造周期、 降低制造成本的目的, 具有重要的理论意 义和重大的实际应用价值。
在高强韧铸造铝合金的发展过程中,法国于 20世纪初研制成功的 A-U5GT占有重要的地位, 在目前具有代表性的高强韧铸造铝合金中它的历史最久、 应用最为广泛。 我国目前没有与它 对应的牌号。
美国铝协会牌号 201. 0 ( 1986年)和 206. 0 ( 1967年)后是在 A-U5GT基础上改造而形成的, 具有很好的力学性能和抗应力腐蚀能力。 但由于含有 0. 4 %〜1. 0 %的银, 材料成本很高, 仅 用于军事或其他要求髙的领域, 限制了其应用范围。
在高强韧铸造铝合金领域, 我国取得了世界瞩目的成绩。 60年代至 70年代, 北京航空材 料研究院研制成功了 ZL205A合金。 ZL205A合金成分复杂, 含有 Cu, Mn, Zr, V, Cd, Ti, B等 7 种合金元素。 ZL205A ( T6 ) 的抗拉强度为 510MPa, 是目前已有注册牌号的铸造铝合金材料强 度最高的。 ZL205A ( T5) 的强韧性最好, 延伸率可达 13 %。 但 ZL205A最大的缺陷是铸造性能 差、 热裂倾向性大, 同时因配方成本高, 应用范围小。
上述 3种高强韧铸造铝合金同属于 Al-Cu系。 该系列合金强度高, 塑性和扨性也较好。 但 铸造性能较差, 具体表现为热裂倾向大、 流动性较差、 补缩困难。 此外, 该系列合金抗蚀性 能较差, 有晶间腐蚀倾向。 该系列合金的铸造成品率很低。
此外, 已经公开的申请号为 200810302670. 3、 200810302668. 6、 200810302669. 0和 200810302671. 8的 4个专利名称均为"一种高强度铸造铝合金材料 "的文献中介绍了一种由 Cu、 Mn、 Ti、 Cr、 Cd、 Zr、 B和稀土元素组成的高强度铸造铝合金材料, 这种铝合金材料具有较高 的抗拉强度和延伸率, 抗拉强度达到了 44( pa, 延伸率大于 6 % ; 但此类高强度铸造铝合金材 料在使用过程中仍未能解决热裂倾向大的问题、 合金强度与可铸性的矛盾突出, 其主要原因 是在合金主元素 Cu、 Mn成分范围, 合金准固相温度范围较宽, 铸造凝固时为具有各向异性的 枝晶发育提供了充分条件, 在凝固后期形成强大的内部收缩应力, 故而收缩热裂倾向大。
目前正式注册的 2XXX系变形铝合金牌号有 70多个, 绝大多数是美国注册的, 其中只有 2001 , 2004, 2011、 2011A、 2111、 2219、 2319、 2419、 2519、 2021、 2A16、 2A17、 2A20、 2B16 等 14个牌号是铜含量在 5%以上的高铜铝合金,而其中铜含量在 6%以上的只有 2A16、 2A17、 2A20、 2B16这 4个牌号。 这些变形铝合金配方中都含有较多的 Si、 Mg、 Zn等成分, 而没有稀土 (RE) 等起微合金化作用的元素, 因此其配方组成与 2系铸造铝合金相差甚远, 反映出两种属性的铝 合金不同的生产工艺和深加工工艺。
2、 高温铝合金
高温合金又称耐热高强合金、热强合金或超合金, 是在 20世纪 40年代随着航空涡轮发动 机的出现发展起来的一种重要金属材料, 能在高温氧化气氛和燃气腐蚀条件下长期承受较大 的工作负荷, 主要用于燃气轮机的热端部件, 是航空航天、 舰船、 发电、 石油化工和交通运 输工业的重要结构材料。 其中有些合金亦可用于生物工程作骨科和齿科材料。 常用的高温合金包括镍基、铁基和钴基合金, 能在 600〜110(TC高温环境下工作; 而耐热 铝合金则是冷战期间发展起来的。耐热高强铝合金适于在 400 °C以下的热环境中长期承受较大 的工作载荷, 在航空航天、 重工机械等领域得到越来越多的应用。 除航空涡轮发动机、 燃气 轮机等直接与高温燃气接触的部件之外, 其余高温高压强动力部件均可采用耐热高强铝合金 铸造。
由于铝合金比较容易加工, 随着加工技术水平的提高, 在强度满足要求的情况下, 人们 越来越多地采用变形铝合金替代铸造铝合金。 因此耐热高强铝合金又分为铸造用合金和变形 用合金两大类。
一般说来, 耐热高强合金都含有多种合金化元素, 多的达十余种。 所加入的元素在合金 中分别起固溶强化、 弥散强化、 晶界强化和表面稳定化等作用, 使合金能在高温下保持高的 力学性能和环境性能。
选用铸造用高温合金时应考虑的因素:
( 1)铸件的正常工作温度、 最高和最低的工作温度以及温度变化的频率。
(2)铸件本身的温差范围及合金的膨胀性能。
(3)铸件承受的载荷性能, 加载、 支承和外部约束方式。
(4)对铸件的寿命要求和容许的变形量、 工作环境和性质、 成形方法和成本因素等。 目前用于高温零部件铸造的铝合金材料, 国家标准中只有 A20 L 0、 ZL206、 ZL207 , ZL208、
206. 0几种牌号, 包括铝铜锰系合金及铝稀土系合金; 其中, 铝铜锰系合金多数以高纯级铝锭 为合金材料, 成本较高, 而铝稀土系合金则在室温下力学性能相对较差。 而且, 目前耐热高 强铝合金普遍存在着高温强度低 (250°C以上瞬时抗拉强度小于 200Mpa, 持久强度小于 lOOMpa) , 配方成本高、 铸造性能差、 铸件合格率低、 废品料及渣料回用性差等缺陷, 造成铸 件质量差、 成本高、 渣料处理流程长等问题。 此外, 近年来申报的多数耐热铝合金专利新配 方中也都含有贵重元素, 而且铸造性能差, 质量无法满足航空技术进歩的要求, 不适于产业 化生产应用。
而在国民经济和国防现代化建设和发展中具有广泛用途和极光明前景的耐热高强变形铝 合金, 国内外文献中报导较少, 己知的 2219、 2A02、 2崩、 2A06、 2A10、 2A11、 2A12、 2A14、 2A16、 2A17. 2A50、 2A70、 2A80等 2XXX系变形铝合金及 7A04等 7XXX系变形铝合金, 在 250 °C以 上温度下强度多数小于 100 Mpa, 而其主要合金元素除 Cu、 Mn外, 都是以 Si、 Mg、 Zn作为主微 合金化元素, 而不添加这几种元素、 且 250°C以上温度下强度在 150 Mpa以上的耐热高强变形 铝合金材料未见报导。
综上所述, 可知目前国内外在耐热高强度铝合金领域研究中存在的问题有: 高温强度和 耐久性不足, 25CTC以上高温瞬时强度均小于 250Mpa, 高温持久强度均小于 100 Mpa; 材料加 工性能差; 废料处理流程长、 成本高, 无法满足航空技术进步的要求等。 发明内容
本发明所要解决的技术问题是, 针对目前高强度铝合金领域存在的熔体处理工艺粗放、 质量差、 热裂倾向大、 铸造性能差, 制品成品率低、 高温强度低、 废品料及渣料回用性差等 技术难题, 以优质熔体、 固溶体和相图理论为指导, 通过优选合金主元素 Cu、 Μη及稀土元素 配方, 降低合金准固相温度范围, 解决铸造时热裂倾向大、 制品高温强度低 (包括瞬时强度 和持久强度) 的带有普遍性的问题; 优选低成本多元微合金化元素配方, 为固溶体中高温相 和强化相的培育和细晶化作用创造物质基础条件; 以及优化熔炼、 热处理工艺技术, 实现固 溶体中高温相和强化相的足量培育和细晶化作用的充分发挥。 最终研制出一种稀土多元微合 金化的 AlCu系新型高强耐热 (铸造性和变形性)铝合金材料。
本发明的技术方案是, 按重量百分比计, 该合金成分为01: 1. 0〜10. 0%, Mn : 0. 05〜1. 5%, Cd : 0. 01〜0· 5%, Ti : 0. 01〜0· 5%, Β : 0· (Π〜0· 2%, Zr : 0· 01〜1. 0%, Co: 0· 01〜1. 0%, RE: 0. 05〜5%, 其余为 Al。
上述的稀土元素 RE为单一稀土元素或一种以上的混合稀土元素。
上述的稀土元素 RE包括 La、 Ce、 Pr、 Nd、 Er、 Ει^[]Υ。
该新型高强耐热铝合金材料的制备方法包括如下步骤:
(1)在上述元素比例范围内, 选定一组可行的元素比例, 再根据需要配制的合金总量, 推算出所需的每种单质金属的质量, 或者中间合金的质量, 或者混合金属添加剂 (包括盐类化 合物)的质量, 编制合金生产配料表, 并按配料表选足备料。
(2)往熔炼炉中加入适量的铝锭或熔融铝液, 加热使之完全融化并在 700〜80(TC下保温; 为防止熔体吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3)再按配方比例先加入 Mn、 Ti、 Zr、 Co纯金属或 Al-Mn、 Al-Ti、 Al-Zr、 Al-Co中间合金 或者混合金属添加剂 (包括盐类化合物), 搅拌均匀后再加入 Cu、 Cd纯金属或 Al-Cu、 Al-Cd中 间合金或者混合金属添加剂 (包括盐类化合物), 再加入 B和稀土元素 RE, 搅拌均匀。
其中, 混合金属添加剂是指添加、调整合金组元用的饼状或块状非烧结性粉末冶金制品。 粉末冶金制品包括锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成; 熔剂是指碱金属或碱 土金属卤素盐类的混合物 (如 NaCl、 KC1、 Na3AlF6等)
(4)然后对上述合金熔体进行炉内精炼; 往合金熔体中加入精炼剂 (可根据不同工况采用 氯气、 六氯乙烷、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜850 °C, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)为了防止材料过烧, 确定对铸件进行 470〜560t;、 30小时以内的固溶处理。
与现有技术相比, 本发明具有如下主要优点:
解决了目前 Al-Cu系高强韧铝合金 (ZL20 LA、 ZL 204A、 ZL 205A等) 大多采用精铝为基体 原料并加入千分之一以上贵重元素,成本较高,导致 Al-Cu系高强韧铝合金只能用于航空航天、 国防军工等尖端领域, 民用领域因性价比不高而应用受限的问题。
随着中国和世界铝产量的快速增长和铝产业规模在中国的不断扩大, "以铝代钢" 日渐 成为产业发展的趋势和潮流, 而在民用领域也迫切需要性价比高的高强韧铝合金; 本发明通 过采用普铝为基体原料, 不加 (或少加) 贵重元素, 优选特征微合金化元素配方, 以及采用 集约、 简练的熔铸、 净化等工艺, 研制出新型高强耐热铝合金材料, 克服了现有材料的在成 本上的门槛。
具体说来, 本发明具有以下八个优点。
1、 高强度和高硬度。 从材料强度看, 在满足塑性要求前提下, 可通过热处理等工艺技术 手段, 使各种强化相在铸态组织中充分、 均匀、 合理析出和分布, 使材料强度达到 480〜540 MPa, 硬度 HB140。
2、 材料的双重属性。 从材料用途属性上看, 它属于两性铝合金, 既有铸造铝合金的特性 又有变形铝合金的特性, 既可以直接用于铸造各类轻强功能件和结构件, 也可以先铸成棒材 再进行热挤压成为各种断面的型材。
本质上, 该材料属于多元微合金化的铸造铝合金, 但由于材料具有极好的流动性及晶间 自润滑性能, 使其同时具备了变形铝合金的易加工特性。
3、 工艺的先进性。 从生产工艺上看, 在熔炼技术上改变了传统的粗放工艺, 可使用电炉 进行严密的保护性熔炼, 从而避免了熔体混入过多的杂质和气体, 既保持了合金的纯净度, 也简化和缩短了复杂的后续熔体处理流程; 同时, 熔炼过程较传统反射式熔炼工艺大大提高 了能源利用率并降低了对环境的污染, 属于绿色环保节能型工艺。
(1)保护性熔炼显著降低了能耗、 污染, 简化了生产流程, 提高了集约化程度 由于铝及铝合金熔体具有极强的吸气倾向, 故在敞开式或封闭性不好的炉内融化和熔炼 时, 熔融的合金液会大量地吸收空气中的 ¾、 水分等气体, 生成不溶性的 A1203和具有良好活 性的 , 在熔体中形成杂质和气体, 如果不及时除去, 会在铸造时形成铸件的夹渣、 气孔、 疏松等缺陷, 导致制品报废; 其中尤其以熔体中 的危害最大, 因为 在铝及铝合金熔融态时 的溶解度大大高于固态时的溶解度, 因此在凝固时, 会有大量的 从合金中逸出造成大量缺 陷。 而不溶性渣则相对较易除去。 因此, 避免熔体吸气是保持熔体质量和铸造质量的重要措 施。
普通的大型工业铝合金熔炼炉是以液体或气体燃料为能源的反射式加热炉或保温炉, 需 要大量的空气助燃, 同时燃烧产物中含有大量水蒸汽和 C02、 (^等物质, 在高温下极易与铝发 生化学反应而生成各种有害杂质, 同时这些杂质本身与铝液一样极易吸附 , 使熔体受到严 重污染, 在进行铸造之前, 熔体必须经历一道或几道专门的净化工序, 并经取样检测合格后 方可进入铸造流程, 这无疑延长了作业流程, 能耗和污染指标都难以降低; 同时因为生产的 连续性要求, 必须使装备大型化, 增加了投资, 提高了技术准入门槛; 而设备的大修成本、 启动成本均随着设备的大型化和长流程而成倍增长。
而一般的铝合金铸造件生产车间, 由于产量规模小, 设备简单粗放, 对铝合金熔体很少 采取密闭保护措施, 同样造成熔体质量和铸造质量不高。
本发明要求的制备方法, 其熔炼方式是采用带密封盖的感应电热设备, 根除了燃料燃烧 时空气、 水蒸汽和各种燃烧产物对熔体的污染, 同时在熔炼过程中, 可采用保护性气体进行 保护气氛熔炼, 最大程度地隔绝空气的侵袭; 由于保持了熔体的高纯洁性, 在其后的铸造阶 段可采取很简单的通过式除气、 除渣装置, 而不必添加专门的停留式保温净化设备, 从而大 大简化了工艺流程。
(2)优化了铸件的热处理工艺, 避免了因 "过烧"而造成的材料力学性能降低、 制品报废 的发生
申请号为 200810302670. 3、 200810302668. 6、 200810302669. 0和 200810302671. 8的 4个专 利名称均为 "一种高强度铸造铝合金材料" 的发明中, 规定材料的热处理工艺参数为 " 620 Ό以下、 72小时以内",在材料应用试验中, 发现固溶处理时温度超 560Ό时, 常常会发生"过 烧"现象, 造成材料微观结构的破坏, 其典型特征是强度和延展性等主要指标显著降低, 铸 件变脆, 表面发黑发暗, 甚至在热处理过程中即产生裂纹、 变形而报废。 而当固溶温度低于 470 °C时, 由于强化相的培育、 析出强化作用不充分, 材料的强度难以达到期望的目标值; 同 时, 在经过多次试验摸索后, 发现热处理时间超过 30小时, 对材料性能的提高没有显著效果。 因此, 为了提高效果和效率, 将热处理工艺参数优化调整为: 470〜560°C、 30小时以内的固 溶处理。
4、 配方的科学性和经济性。从原料来源上看, 先进的配方创造了两方面的优势一基体材 料优势和合金元素优势。 一方面, 新材料系列的基体合金可以采用普通工业纯铝(即双零铝, 包括铝液和重熔用铝锭),比已有的高强度铝合金必须釆用精铝或高纯级铝为基体合金的配方 模式, 具有原料供应充足、 成本低、 采购方便等优势; 同时, 该材料同样可以采用精铝或高 纯级铝作为基体合金, 而这种配方的材料比该品种的普铝基材料具有更高的延展性。 另一方 面, 因贵重元素对合金成本升高的贡献率是普通元素的数十乃至百倍以上, 新材料系列的合 金元素组合中多数不采用贵重元素, 即使采用, 比例也很小, 均在千分之一以下; 而已有的 高强度铝合金贵重元素的比例均在千分之一以上, 两方面的优势为系列新材料拓展市场储备 了巨大潜力。
本发明通过优选合金主元素铜 (Cu)、锰 (Mn)和以钴 (Co)为特征微合金化元素的多元配方, 为固溶体中高温相和强化相的培育和细晶化作用创造物质基础条件, 合金在主元素 Cu、 Mn形 成强化 e (Al2Cu)、 T相 (Al12Mn2Cu) 的基础上, 选用高温元素钴(Co)和 RE作为复杂合金化的 微量添加元素, Co在合金中形成 AlCo、 190)2等8种弥散性高温强化相, Co是复杂合金化的高 强度铸造铝合金的微量添加元素。 它与 Ni、 Mn共存时, 形成 Al4 (NiCoFeMn) 等很复杂的强化 相于枝晶间, 阻碍位错、 阻止晶粒滑移, 有效地提高了合金的室温和高温 (40CTC下) 强度。 稀土 (RE)在合金中形成多种金属化合物弥散性高温强化相 (例如: 稀土 Ce在合金中形成 α— Ce3Alu〜 β— Ce3Al等 7种金属化合物; 稀土 La在合金中形成 α— A1UL¾〜 β 1UL 等 6种金属化 合物; 稀土 Pr在合金中形成 α— Al„Pr3〜f3— AluPr3等 6种金属化合物; 稀土 Nd在合金中形 成 a _AluNd3〜e _ Al uNd3等 6种金属化合物;稀土 Er在合金中形成 ErAl3、ErAl2、ErAl、Er3Al2、 Er2Al等 5种金属化合物; 稀土 Y在合金中形成 A13Y、 A12Y、 Al Y、 Al2 Υ3、 Α1 等5种金属化合 物; 稀土 Dy在合金中形成 α— DyAl3〜P— DyAl3等 6种金属化合物; 稀土 Eu在合金中形成 EuAl4、 EuAl2、 EuAl等 3种金属化合物; 稀土 Sm在合金中形成 Al uSrn^ Al3Sm、 Al2Sm、 Al Sm、 Al 5!¾等5种金属化合物; 稀土 Pm在合金中形成 Al l lPm3、 1?1¾等5种难熔活性金属化合物; 稀 土 Gd在合金中形成 Al4Gd、 A117Gd2等 7种难熔活性金属化合物; 稀土 Gd在合金中形成 Al3Tb、 AlTb2等5种难熔活性金属化合物; 稀土 Ho在合金中形成 Al3Ho、 1 2等5种难熔活性金属化合 物; 稀土 Tm在合金中形成 Al3Tm、 AlTm等 3种难熔活性金属化合物; 稀土 Yb 在合金中形成 Al3Yb、 Al2Yb等 2种难熔活性金属化合物; 稀土 Lu在合金中形成 Al3Lu、 11^2等5种难熔活性金 属化合物等等) , 都提高了合金的室温强度、 耐热强度和熔体流动性。
本发明的主合金元素作用机理如下。
①该材料允许铜(Cu)含量在 1〜10%范围,较 Al-Cu系铸造铝合金含铜 (Cu)量为 3〜11%的范 围略有不同, 但在理论上则具有极为重大的创新意义。
一方面, 在铜(Cu)含量为 5. 65〜5. 7%时, 正好等于 Cu在 Al-Cu合金中的共晶溶解度, 在热 处理过程中按照 "完全固溶一均匀析出一晶界强化相一晶隙填充剂 (粘结、 镶嵌、 防滑)" 的 转变模式和作用机理变化, 形成较多的富 Cu 强化相 (其中包括 Al2Cu即 3相), 从而使铝合金的 室温和高温力学性能都大大提高, 也改善了加工性能; 但由于 Cu在 A1中的溶解度随温度降低 而急剧下降, 在结晶凝固过程中, 01[1 _ 1固溶体中的过饱和度快速提高, α— A1枝晶一 边长大, 一边强烈增加地向晶界外排出富 Cu强化相的倾向, 造成晶内和晶界间巨大的结构应 力, 同时合金整体正处于凝固收缩阶段, 收缩应力与结构应力叠加在一起, 当超过合金的即 时实际强度, 则形成热裂纹, 因此在铜 (Cu)含量 5. 65%的一定范围内, 铝合金的铸造性能最 差、 热裂倾向性最大。 但总的趋势是, 随着铜含量的降低, 合金的热裂倾向性也降低; 当 Cu 含量 < 1%时, 其强化相不足, 强化相的转变模式和作用机理难以充分发挥, 在温度变化时在 晶界的析出和向晶内的溶入会形成晶界间较多的缺陷, 降低合金的室温和高温强度, 所以 Cu 含量过低, 对简单的 Al-Cu合金来说没有意义; 但如果合金中加入了较多的稀土元素( E), 则 可以起到弥补 Cu含量过低的特殊效果。
另一方面, 在 Cu含量; ^5. 7%时, 富 Cu相在热处理时不能被基体全部吸收, 则以边界富 Cu 金属化合物形态弥散分布于晶界, 降低了 α— A1固溶体内外 Cu质点的浓度差, 在凝固过程中 平缓了 α— A1固溶体枝晶向晶界排出富 Cu相的强度, 即降低了结构应力和热裂倾向。 显然, 当 Cu含量 5. 7%, 富 Cu相越多, 结晶时合金内部的结构应力和热裂倾向越小; 同时, 高熔点 细晶弥散的富 Cu相在熔体结晶时形成活性异质晶核, 加速熔体结晶反应但又阻止晶核长大, 细化了晶粒, 也降低了合金热裂倾向性; 并使基体晶界之间充填更加饱满; 富 Cu相还能与 Al、 Mn等多种元素形成难熔金属化合物。 所有这些作用, 明显地弱化了熔体的表面张力, 降低了 熔体粘度, 从而显著提高了熔体流动性及合金的铸造性能。
当 Cu含量处于 5. 7%左右时, 经热处理后, 在基体晶界有较多的富 Cu相 (溶入一析出相)与 较少的(约 0. 5%) Cu基金属化合物细晶弥散相, 使室温状态下的合金强度保持较高水平, 但当 处于高温环境时, 因大量富 Cu相重新溶入基体中, 就会造成较多的晶间空隙和缺陷, 这会使 合金的高温强度显著下降。 随着 Cu含量继续增加, 合金强度受温度影响的程度减小, 而当弥 散相与析出相基本处于等量状态时, 材料强度受温度变化的影响最低, 此时合金中 Cu含量应 为 11〜12%。
但当合金中 Cu含量〉 10%时,因结晶时过剩的 Cu相具有优先结晶性质而形成巨大的网络结 构, 合金粘度大大增强, 过剩相在结晶过程中取代铝基体成为控制结晶的主要因素, 原有弥 散相对铝基体相的优良作用全部受到屏蔽, 因此合金的各种性能又大幅下降。
根据以上理论基础及实践的验证, 确定主合金元素 Cu含量的合理范围为: l〜10% (wt%;)。 ②该材料以锰 (Mn)元素改善抗蚀性, 同时屏蔽杂质 Fe, 减少 Fe的有害作用。 因锰 (Mn)元素与基体作用生成的 ΜηΑ16与纯铝具有相同的电位, 可以有效地改善合金的抗 蚀性和焊接性; 同时 Mn作为高温强化相, 具有提高再结晶温度、抑制再结晶晶粒粗化的作用, 能够实现对合金的固溶强化、 补充强化、 提高耐热性能; 在晶粒细化剂作用下, 能与 Fe元素 生成球团状的 Al3 (Fe、 Mn), 有效消除了 Fe对合金的有害作用, 因此本发明可允许 Fe含量在较 宽的范围 (FesSO. 5%) , 这样带来的好处是: 实现普铝代替精铝, 降低成本, 扩大原料来源 及材料应用领域.。
③主要使用稀土 RE作为基础微合金化元素, 且其含量范围大, 最高可达 5%, 可充分发挥 稀土元素在合金中的除气、 除渣、 净化作用、 细化晶粒和变质作用、 提高合金的力学性能以 及耐蚀性作用。
稀土元素除气、 除渣、 净化作用的机理是: 稀土元素在活性很强, 对氧、 氢、 硫、 氮等 具有较强的亲和力,其脱氧能力超过现有最强的脱氧剂铝,可把含量为 50*10- 6氧,脱至 10*10- 6 以下, 其脱硫作用可把含 S量为 20*10— 6脱至 1〜5*10— 6。 因此, 含稀土的铝合金在熔炼时很容易 和铝液中的上述物质发生化学反应, 反应产物不溶于铝而进入渣中, 从而使合金中的气体含 量降低, 使合金产品产生气孔和缩松的倾向大大降低。
稀土元素能显著提高合金的力学性能。 稀土元素在铝合金中可形成稳定的高熔点金属间 化合物如 A14RE、 Al8CuRE、 Al8Mn4RE、 Al24R Mn等。 这些高熔点金属间化合物弥散分布于呈网 状或骨架状的晶间和枝晶间, 并与基体牢固结合, 起到了强化和稳定晶界的作用。 同时, 合 金中还形成一定数量的 AlSiRE相, 由于其熔点和硬度很高, 因此对提高合金的耐热性和耐磨 性均有良好的作用。 此外, 还可中和金属液中的低熔点杂质元素 Sn、 Pb、 Sb等, 与它们形成 高熔点的化合物或使他们从枝晶间向整个晶体内均匀分布, 消除了枝晶组织。
稀土元素有细化晶粒和变质作用。 稀土元素为表面活性元素, 可集中分布在晶界面上, 降低熔体粘度, 增强流动性, 降低相与相之间的拉力, 因为使形成临界尺寸晶核的功减少, 结晶核数量增加, 从而使晶粒细化。 稀土对铝合金的变质作用具有长效性和重熔稳定性, 大 多数单一或混合稀土加入后对 α〜Α1相有很强的细化和变质作用。
此外, 稀土元素还能够提高合金的导电性。 由于稀土能细化铝晶粒, 也能在合金中 Fe、 Si等杂质形成稳定的化合物 (如 CeFe5、 CeSi、 CeSi2等) 并从晶内析出, 再加上稀土对合金的 净化作用, 使得铝的电阻率得到降低, 导电性提高 (约 2%) 。
很少量的稀土元素 RE即可对合金性能产生明显的变质改良作用, 因此, 一般铝合金的稀 土加入量在 1%以下,在 200810302670. 3、 200810302668. 6、 200810302669. 0和 200810302671. 8 专利申请中, 稀土含量确定为0. 05〜0. 3%。 A人 A1-RE合金相图分析, 由于大部分稀土在铝中的 溶解度很小(如 Ce约为 0. 01%), 其存在形态多以高熔点金属间化合物分布于晶界或基晶内部。 由于活性很高, 在熔体净化中充当净化剂消耗掉一部分, 若加入量太少, 则其对 α〜Α1相的 变质作用就难以充分发挥。 为保持稀土变质作用的长效性和重熔稳定性, 并充分发挥其高温 强化特性, 本发明特把铜含量与稀土含量一起考虑, 确定其含量范围为 0. 05〜5%。
④钴 (Co)元素作为复杂合金化的特征添加元素, 在合金中能形成 AlCo、 19(¾等8种金属 化合物, 呈弥散相分布于基体晶界, 提髙合金的室温和高温强度。
5、 优异的铸造性能。 通过在高科技结构、 航空、 航天、 民用重工等几个领域使用的铸件 多次铸造试验, 验证了该新材料的优异性能: 铸造性能高于目前的 A201. 0、 ZL206 , ZL207、 ZL208、 206. 0等高强度铸造铝合金, 解决了上述铝合金铸造时热裂倾向性大、 铸件合格率低 的重大问题; 旧料回炉重熔与新料可实现任意比例配料, 新旧料混合熔体浇注性能无改变, 且有稳定材料强度、 提高延展性的良好作用, 较原有高强度铝合金废料回用性差、 循环路线 长的状况, 具有极显著的经济性和集约性。
新材料消除热裂倾向的原理在于: 因合金中铜含量增多形成富 Cu相, 富 Cu相作为高熔点 细晶弥散相以金属化合物形态弥散分布于晶界, 在熔体结晶时有效抵消了晶粒内富 Cu溶质因 过饱和度急剧升高而形成的向晶界扩散的强烈倾向, 从而减缓了结晶时的结构应力; 同时晶 界上富 Cu弥散相与 Co稀土微合金化元素及 Mn、 Zr、 Ti、 B等元素的多种弥散相, 都具有细化晶 粒、 充填基体晶界、 形成近铝电位金属化合物的多种作用, 所有这些作用明显地弱化了熔体 的表面张力, 降低了熔体粘度, 从而显著提高了熔体流动性及合金的铸造性能, 保证了铸造 产品具有较高的合格率。
旧料回用性好的原理在于: 本发明中多元微合金化作用具有长效性和重熔稳定性, 重熔 时, 熔体的结构特性保持了一次合金熔体形成的原子集团结构和细晶结构, 大量的活性晶核 能够在熔体中充分发挥凝聚、 同化微晶结构的作用, 并能保持原有的流动性。 因此, 旧料的 配入有稳定材料强度、 提高延展性的良好作用。
旧料的这种特性, 完全可以实现在生产现场的即时回用, 无论是渣料、 加工余料还是不 合格铸件, 均可与新料一同熔炼或直接加入熔体中。
本发明的此种特性, 较目前大量应用的 1XXX系和 2XXX系高高强度铝合金材料铸造成品率 显著提高, 大大降低了废品量, 因此在生产现场不需要大的废品堆场 (实际生产中, 铝合金铸 造车间往往要规划出很大的废品堆放场地); 同时, 很多铸造铝合金不具备重熔稳定性, 无法 在现场直接回用, 因此需要组批进行集中处理, 占据很大的制造成本, 衍生出一系列处理环 节和无效劳动; 而应用本发明提供的新材料, 所有这些额外的环节、 成本和无效劳动均可省 去。
6、 优异的加工、 表面防腐处理性能。 通过将新材料加工成轴、 球、 管、 角材、 螺栓等各 种形状的成品件的试验, 证明材料具有极好的可加工性能,表面可达到近镜面程度的精洁度, 光反射率高于纯铝; 表面氧化和涂覆试验表明, 表面阳极氧化后膜厚可达到标准要求等级、 表面颜色无改变, 涂料与氧化表面的附着性完全达到抗破坏性试验的标准等级。
7、 优异的高温性能。 该材料具有高温铝合金的特性, 可以达到 40CTC条件下强度高于 200Mpa以上, 高于传统的高温 (耐热)铝合金材料, 这一特性使新材料可以替代除航空发动机 匣体直接承受高温燃气灼烧的部件之外的其它各部位耐热部件材料。 (耐热性原理参见特性 4
"配方的科学性和经济性" 中关于富铜相、 稀土 (RE;)、 耐热合金元素 Co的内容) 。
8、典型的原创性。该系列新型材料是申请人在取得合金化理论创新突破后快速研发出来 的, 材料优异性质的验证同时就是对新合金化理论的验证, 而这种理论突破目前在所有的文 献资料上都没有明确记载过, 因此该系列新材料在国际上属于原始性、 基础性的重大创新。
本发明的创新点
表一列出了与本发明在某一方面的性能和用途上相近的 31种铝合金的元素组成。 可以看 出, 与己有各种高铜含量变形铝合金、 耐热变形铝合金、 耐热铸造铝合金相比, 本发明主要 有以下创新内容。
一是铜 (Cu)含量允许范围大, 在 1〜10%; 同时以锰 (Mn)元素配合形成多种高温强化相。 二是主要使用稀土 (RE)作为基础微合金化元素, 且其含量范围大, 最高可达 5%, 可充分 发挥稀土 (RE)在合金中的除气、 除渣、 净化作用、 细化晶粒和变质作用、 提高合金的力学性 能以及耐蚀性作用; 稀土元素对氧、 硫、 氮、 氢的亲和力都很强, 因而其脱氧、 脱硫、 去除 氢气和氮气的作用都很强, 此外, 稀土 (RE)为表面活性元素, 可集中分布在晶界面上, 降低 相与相之间的拉力, 因为使形成临界尺寸晶核的功减少, 结晶核数量增加, 从而使晶粒细化。
三是对铁元素的限制比较宽松, 允许其含量最大可达 0. 5%, 这为使用普铝为基体进行合 金材熔铸开拓了空间。
四是不使用镁、 锌等低熔点元素作为产生强化相的物质, 避免了高温下材料强化相的分 解和转化, 从而显著提高了材料的高温强度。
五是以钴 (Co)元素作为复杂合金化的特征添加元素, 在合金中能形成 AlCo、 人1^02等8种 金属化合物, 在熔体中呈弥散相分布于基体晶界, 提高合金的室温和高温强度。 结合使用钛 ( Ti ) 、 硼 (B) 、 锆 (Zr) 元素作为综合晶粒细化剂, 使合金材料具备了高强高韧耐热和熔 体高流动性等全部优良性能的物质基础。
以上是本发明特征配方中最明显的五个方面。
表一 与本发明有关的各种铝合金化学成分
Figure imgf000013_0001
Figure imgf000014_0001
力学性能比较
申请人将本发明与现有几种高强韧铝合金的力学性能进行对比, 见表二。
Figure imgf000014_0002
R T5 358〜450 4. 0〜7. 0
ZL107A J T5 420〜470 4〜6
本发明 J. s T6 480—540 3〜8 140
①所列数据是高纯的 206. 0合金, 即 W ( Si ) 0. 05%, W ( Fe ) 0. 10%。 S-砂型铸造, J- 金属型铸造, R-熔模铸造
从表二可以看出, 本发明的抗拉强度 480〜540 MPa, 硬度大于 HB140, 明显优于现有高强 韧铝合金的力学性能。
3、 高温性能
申请人对本发明在各种温度条件下的强度高温持久性能进行了测试, 并与现有常用耐热 铝合金的高温持久性能进行了对比, 见表三。
Figure imgf000015_0001
从表三可以看出, 本发明的室温强度大于 450Mpa, 高温强度 250°C时在 300Mpa以上, 高温 强度 30(TC时, 高温持久性能大于 200 Mpa, 明显优于已有耐热高强合金的高温持久性。
综上所述, 本发明新型高强耐热铝合金材料具有高科技含量、 广袤的应用领域和极佳的 市场前景, 其极优的性价比使其可以替代目前几乎所有高强度铝合金和高温铝合金, 代表了 中国乃至世界轻强结构材料的发展方向。 具体实施方式
实施例 1 : Cu-1. 0%, 特征微合金化元素 -Co, 基础微合金化稀土元素 -La
(1)按配料计算表称量好所需的各种合金元素, 如下。 元素 铝 Al 铜 Cu 锰 Mn 镉 Cd 锆 Zr 钴 Co 钛 Ti La 硼 B 质量 (g) 7156 80 120 36 80 80 40 400 8 合计 8000 (g)
(2)往熔炼炉中加入适量的铝锭,加热使之完全融化并在 700〜800°C下保温; 为防止熔体 吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3) 再按配方比例先加入 Al-Mn、 Al-Ti、 Al-Co、 Al-Zr中间合金或者混合金属添加剂(包 括盐类化合物), 搅拌均匀后再加入 Cu纯金属及 Al-Cd中间合金或者混合金属添加剂, 再加入 B 和稀土元素 La, 搅拌均匀。
混合金属添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品, 包括锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。 熔剂是指碱金属或碱土金属卤素盐 类的混合物, 包括 NaCl、 KC1和 Na3AlF6
(4)然后对上述合金熔体进行炉内精炼;往合金熔体中加入精炼剂 (可根据不同工况釆用 氯气、 六氯乙烷、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜85(TC, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)对铸件进行 470〜560°C、 30小时以内的固溶处理。
(8)试样指标: 抗拉强度 485Mpa, 延伸率 8%。
实施例 2: Cu-4. 2%, 特征微合金化元素 -Co, 基础微合金化稀土元素 -La、 Ce混合稀土
Figure imgf000016_0001
(2)往熔炼炉中加入适量的铝锭,加热使之完全融化并在 700~800°C下保温; 为防止熔体 吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3) 再按配方比例先加入 Al-Mn、 Al-Ti、 Al-Co, Al-Zr中间合金或者混合金属添加剂(包 括盐类化合物), 搅拌均匀后再加入 Cu纯金属及 Al-Cd中间合金或者混合金属添加剂, 再加入 B 和稀土元素 La、 Ce混合稀土, 搅拌均匀。
混合金属添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品, 包括 锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。 熔剂是指碱金属或碱土金属卤素盐类的 混合物, 包括 NaCl、 KC1和 N¾A1F6。 (4)然后对上述合金熔体进行炉内精炼;往合金熔体中加入精炼剂 (可根据不同工况采用 氯气、 六氯乙垸、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜850Ό, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)对铸件进行 470〜560°C、 30小时以内的固溶处理。
(8)试样指标: 抗拉强度 525Mpa, 延伸率 6. 2%。
实施例 3: Cu-6. 01%, 特征微合金化元素 -Co, 基础微合金化稀土元素 -La、 Ce、 Pr混合稀 土
Figure imgf000017_0001
(2)往熔炼炉中加入适量的铝锭,加热使之完全融化并在 700〜80(TC下保温; 为防止熔体 吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3) 再按配方比例先加入 Al-Mn、 Al-Ti、 Al-Co、 Al-Zr中间合金或者混合金属添加剂(包 括盐类化合物), 搅拌均匀后再加入 Cu纯金属及 Al-Cd中间合金或者混合金属添加剂, 再加入 B 和稀土元素 La、 Ce、 Pr混合稀土, 搅拌均匀。
混合金属添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品, 包括 锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。 熔剂是指碱金属或碱土金属卤素盐类的 混合物, 包括 NaCl、 KC1和 Na3AlF6
(4)然后对上述合金熔体进行炉内精炼;往合金熔体中加入精炼剂 (可根据不同工况采用 氯气、 六氯乙垸、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜850°C, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)对铸件进行 470〜560°C、 30小时以内的固溶处理。
(8)试样指标: 抗拉强度 535Mpa, 延伸率 5%。
实施例 4: Cu-8%, 特征微合金化元素 -Co, 基础微合金化稀土元素 -Nd
(1)按配料计算表称量好所需的各种合金元素, 如下。 元素 铝 Al 铜 Cu 猛 Mn 镉 Cd 锆 Zr 钴 Co 钛 Ti Nd 硼 B 质量 (g) 7145 640 40 20 40 50 28 30 7 合计 8000 (g)
(2)往熔炼炉中加入适量的铝锭,加热使之完全融化并在 700〜800°C下保温; 为防止熔体 吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3) 再按配方比例先加入 Al-Mn、 Al-Ti、 Al-Co、 Al-Zr中间合金或者混合金属添加剂(包 括盐类化合物), 搅拌均匀后再加入 Cu纯金属及 Al-Cd中间合金或者混合金属添加剂, 再加入 B 和稀土元素 Nd, 搅拌均匀。
混合金属添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品, 包括 锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。 熔剂是指碱金属或碱土金属卤素盐类的 混合物, 包括 NaCl、 KC1和 Na3AlF6
(4)然后对上述合金熔体进行炉内精炼;往合金熔体中加入精炼剂 (可根据不同工况釆用 氯气、 六氯乙烷、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜85(TC, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)对铸件进行 470〜560°C、 30小时以内的固溶处理。
(8)试样指标: 抗拉强度 530Mpa, 延伸率 4%。
实施例 5: Cu-7%, 特征微合金化元素 -Co, 基础微合金化稀土元素 -Er
Figure imgf000018_0001
(2)往熔炼炉中加入适量的铝锭,加热使之完全融化并在 700~800°C下保温; 为防止熔体 吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3) 再按配方比例先加入 Al-Mn、 Al-Ti、 Al-Co, Al-Zr中间合金或者混合金属添加剂(包 括盐类化合物), 搅拌均匀后再加入 Cu纯金属及 Al-Cd中间合金或者混合金属添加剂, 再加入 B 和稀土元素 Er, 搅拌均匀。
混合金属添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品, 包括 锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。 熔剂是指碱金属或碱土金属卤素盐类的 混合物, 包括 NaCl、 KC1和 N¾A1F6。 (4)然后对上述合金熔体进行炉内精炼;往合金熔体中加入精炼剂 (可根据不同工况采用 氯气、 六氯乙垸、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜850Ό, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)对铸件进行 470〜560°C、 30小时以内的固溶处理。
(8)试样指标: 抗拉强度 530Mpa, 延伸率 4. 7%。
实施例 6: Cu-10. 0%, 特征微合金化元素 -Co, 基础微合金化稀土元素 -Y
Figure imgf000019_0001
(2)往熔炼炉中加入适量的铝锭,加热使之完全融化并在 700〜800°C下保温; 为防止熔体 吸入过多的空气, 熔化过程应尽可能在短时间内和封闭环境内完成。
(3) 再按配方比例先加入 Al-Mn、 Al-Ti、 Al-Co、 Al-Zr中间合金或者混合金属添加剂(包 括盐类化合物), 搅拌均匀后再加入 Cu纯金属及 Al-Cd中间合金或者混合金属添加剂, 再加入 B 和稀土元素 Y, 搅拌均匀。
混合金属添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品, 包括 锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。 熔剂是指碱金属或碱土金属卤素盐类的 混合物, 包括 NaCl、 KC1和 N¾A1F6
(4)然后对上述合金熔体进行炉内精炼;往合金熔体中加入精炼剂 (可根据不同工况采用 氯气、 六氯乙烷、 氯化锰等作为精炼剂, 以及硼盐变质剂等), 并搅拌均匀, 同时为防止熔体 吸入水份和烧损, 熔体精炼应尽可能在封闭环境中操作。
(5)精炼后打渣、 静置、 调温至 630〜850°C, 合金液倾倒出炉, 在线除气、 除渣处理。
(6)铸造 (在铸模中结晶凝固)。
(7)对铸件进行 470〜560°C、 30小时以内的固溶处理。
(8)试样指标: 抗拉强度 490Mpa, 延伸率 3%。

Claims

权利要求书
1、一种 Co-RE高强耐热铝合金材料,其特征在于:按重量百分比计,该合金成分为 Cu:1.0〜 10.0%, Mn:0.05〜1.5%, Cd: 0.01〜0.5%, Tl: 0.01〜0.5%, B:0.01〜0.2%, Zr: 0.01〜1.0%, Co:0.01〜1.0%, 稀土元素 RE:0.05〜5%, 其余为 Al。
2、根据权利要求 1所述的 Co-RE高强耐热铝合金材料, 其特征在于: 稀土元素 RE为单一稀 土元素或一种以上的混合稀土元素。
3、 根据权利要求 1或 2所述的 Co-RE高强耐热铝合金材料, 其特征在于: 稀土元素 RE包括
La, Ce、 Pr、 Nd、 Er、 Eu禾口 Y。
4、 一种如权利要求 3所述的 Co-RE高强耐热铝合金材料的制备方法, 其特征在于: 包括如 下步骤:
(1)在上述元素比例范围内, 选定一组元素比例, 再根据需要配制的合金总量, 推算出 所需的每种单质金属的质量, 或者中间合金的质量, 或者混合金属添加剂的质量, 编制合金 生产配料表, 并按配料表选足备料;
(2)往熔炼炉中加入适量的铝锭或熔融铝液,加热使之完全融化并在 700〜800Ό下保温; 熔化过程在封闭环境内完成;
(3)再按配方比例先加入 Mn、 Ti、 Zr、 Co纯金属或 Al-Mn、 Al-Ti、 Al-Zr、 Al-Co中间合 金或者混合金属添加剂, 搅拌均匀后再加入 Cu、 Cd纯金属或 Al-Cu、 Al-Cd中间合金或者混合 金属添加剂, 再加入 B和稀土元素 RE, 搅拌均匀;
(4)然后对上述合金熔体进行炉内精炼; 往合金熔体中加入精炼剂, 并搅拌均匀, 熔体 精炼在封闭环境中操作;
(5) 精炼后打渣、 静置、 调温至 630〜850°C, 合金液倾倒出炉, 在线除气、 除渣处理;
(6) 铸造;
(7) 对铸件进行 470〜560°C、 30小时以内的固溶处理。
5、根据权利要求 4所述的 Co-RE高强耐热铝合金材料的制备方法, 其特征在于: 混合金属 添加剂是指添加、 调整合金组元用的饼状或块状非烧结性粉末冶金制品。
6、根据权利要求 5所述的 Co-RE高强耐热铝合金材料的制备方法, 其特征在于: 粉末冶金 制品包括锰、 铜、 锆、 钴、 硼或钛金属粉末与熔剂混合而成。
7、根据权利要求 6所述的 Co-RE高强耐热铝合金材料的制备方法, 其特征在于: 熔剂是指 碱金属或碱土金属卤素盐类的混合物, 包括 NaCl、 KC1和 N¾A1F6
S、根据权利要求 4所述的 Co-RE高强耐热铝合金材料的制备方法,其特征在于:在步骤(4) 中, 精炼剂是指氯气、 六氯乙烷、 氯化锰以及硼盐变质剂。
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