CN102021383B - Ag-Nb-RE high-strength heat-resisting aluminum alloy material modified by C and preparation method thereof - Google Patents

Abstract

The invention discloses an Ag-Nb-RE high-strength heat-resisting aluminum alloy material modified by C and a preparation method thereof. The Ag-Nb-RE high-strength heat-resisting aluminum alloy material comprises the following components in percentage by weight: 1.0 to 10.0 percent of Cu, 0.05 to 1.5 percent of Mn, 0.01 to 0.5 percent of Cd, 0.01 to 0.5 percent of Ti, 0.0001 to 0.15 percent of C, 0.01 to 1.0 percent of Zr, 0.01 to 1.0 percent of Ag, 0.01 to 1.0 percent of Nb, 0.05 to 5 percent of RE and the balance of Al. In the invention, based on the theory of high-quality melts, sosoloids and phase diagrams, the temperature range of an alloy quasi-solid phase is reduced by selecting formulas of the Cu, Mn and RE main alloy elements preferably, the C is used as a high-efficiency modifier, and thus, the problems of large hot cracking tendencyduring casting, low high-temperature strength of products and the like are solved; and the high-strength heat-resisting aluminum alloy material is developed finally by selecting a formula of low-cost multielement micro-alloying elements preferably.

Description

With rotten Ag-Nb-RE high strength heat resistant alloy material of C and preparation method thereof

Technical field

The present invention relates to a kind of aluminum alloy materials and preparation method thereof, particularly a kind of with rotten Ag-Nb-RE high strength heat resistant alloy material of C and preparation method thereof.

Background technology

Aluminium alloy is a kind of younger metallic substance, just begins industrial application in 20 beginnings of the century.During the World War II, aluminium is mainly for the manufacture of military aircraft.After the war, because war industry is die-offed to the demand of aluminium, the aluminium industry member is just started to develop civil aluminum alloy, make its range of application expand to construction industry, container package industry, transportation, electric power and national economy all departments such as electronic industry, machinery manufacturing industry and petrochemical complex by aircraft industry, be applied in the middle of the daily life.Now, more than the consumption of aluminium, scope is wide, is only second to iron and steel, becomes second largest metallic substance.

From the angle of production and Al-alloy products, traditionally aldural is divided into wrought aluminium alloy and cast aluminium alloy two classes; Divide from the temperature condition that goods can be used, aldural is divided into common aluminum alloy and high temperature (or heat-resisting) aluminium alloy again.Up to the present, can satisfy the high strength at high temperature needs, have only the Al-Cu line aluminium alloy, on trade mark series, Al-Cu is that alloy comprises cast aluminium alloy and wrought aluminium alloy, no matter and casting still is out of shape, all belong to 2 line aluminium alloys; And can satisfy the high-temp and high-strength aluminium alloy that good casting property is carried out deformation processing easily simultaneously, also do not see open the report.

1, high strength cast aluminum alloys and wrought aluminium alloy

General cast aluminium alloy comprises that AlSi system, AlCu system, AlMg system and AlZn are 4 series, wherein the intensity with AlCu system and AlZn line aluminium alloy is the highest, but it is most between 200Mpa～300Mpa, a few trade mark that has only AlCu system that is higher than 400Mpa, but because adopting the refined aluminium matrix and adding noble element, manufacturing cost is very high; AlZn is that the resistance toheat of casting alloy is very poor.Therefore, general cast aluminium alloy is compared with wrought aluminium alloy because obdurability is inferior slightly and is made its range of application be subjected to bigger restriction.Many important use such as extraordinary traction engine bogie wheel, aviation alloyed aluminium etc. adopts wrought aluminium alloy, rather than cast aluminium alloy.Wrought aluminium alloy has reduced defective by means such as extruding, rolling, forgings, refinement crystal grain, improved density, thereby had very high intensity, good toughness and good use properties.But, equipment and moulds of industrial equipment are required height, operation is many, so the wrought aluminium alloy production cycle is long, cost is very high.Compare plurality of advantages such as that cast aluminium alloy has is cheap, organize isotropy, can obtain special organization, be easy to produce complex-shaped part, can small serial production also can produce in enormous quantities with wrought aluminium alloy.Therefore, develop high-toughness casting aluminum alloy material and the casting forming process thereof that can substitute the part wrought aluminium alloy, can reach the purpose of casting and forging, shortening manufacturing cycle, reduction manufacturing cost, have important significance for theories and great actual application value.

In the evolution of high-toughness casting aluminum alloy, the A-U5GT that France succeeded in developing in 20 beginnings of the century occupies an important position, in at present representative high-toughness casting aluminum alloy its history at most, be most widely used, China is the trade mark corresponding with it not at present; Transform on the A-U5GT basis behind the U.S. aluminium association trade mark 201.0 (1986) and 206.0 (1967) and form, have good mechanical property and stress corrosion resistant ability.

In the high-toughness casting aluminum alloy field, China has obtained the achievement of attracting attention in the world.The sixties, the Beijing Research Inst. of Aeronautic Material succeeded in developing the ZL205A alloy to the seventies; ZL205A alloying constituent complexity contains Cu, Mn, Zr, V, Cd, Ti, 7 kinds of alloying elements such as B.The tensile strength of ZL205A (T6) is 510MPa, is that the cast aluminium alloy material intensity of the existing registration trade mark at present is the highest; The obdurability of ZL205A (T5) is best, and unit elongation can reach 13%; But that the defective of ZL205A maximum is castability is poor, hot cracking tendency is big, and simultaneously because of the formulation cost height, range of application is little.

Above-mentioned 3 kinds of high-toughness casting aluminum alloys belong to Al-Cu system.This series alloy intensity height, plasticity and toughness are also better.But castability is relatively poor, is embodied in that hot cracking tendency is big, flowability is relatively poor, feeding is difficult.In addition, this series alloy etch resistant properties is relatively poor, and the intergranular corrosion tendency is arranged.And the qualified casting of this series alloy is very low.

In addition, disclosed application number is that 4 patent names of 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 are in the document of " a kind of high-strength cast aluminium alloy material " and have introduced a kind of high-strength cast aluminium alloy material of being made up of Cu, Mn, Ti, Cr, Cd, Zr, B and rare earth element, this aluminum alloy materials has advantages of higher tensile strength and unit elongation, tensile strength has reached 440Mpa, and unit elongation is greater than 6%; But this type of high-strength cast aluminium alloy material in use still fails to solve the particularly thorny of the big problem of hot cracking tendency, alloy strength and castability, its major cause is at alloy principal element Cu, Mn composition range, the accurate solid-state temperature a wider range of alloy, provide sufficient condition for having anisotropic dendrite growth during casting solidification, form powerful internal contraction stress solidifying the later stage, so it is big to shrink hot cracking tendency.

The 2XXX of official registration is that the wrought aluminium alloy trade mark has more than 70 at present, the overwhelming majority is U.S. Register, wherein have only 2001,2004,2011,14 trades mark such as 2011A, 2111,2219,2319,2419,2519,2021,2A16,2A17,2A20,2B16 be copper content at the high X alloy more than 5%, and wherein copper content is having only 2A16,2A17, these 4 trades mark of 2A20,2B16 more than 6%.All contain compositions such as more Si, Mg, Zn in these wrought aluminium alloy prescriptions, and there is not rare earth (RE) etc. to play the element of microalloying effect, therefore its prescription composition is that cast aluminium alloy differs greatly with 2, reflects different production technique and the deep processing technology of aluminium alloy of two kinds of attributes.

2, high temperature aluminium alloys

Superalloy claims heat-resistance high-strength alloy, the strong alloy of heat or superalloy again, it is a kind of important meals material that grows up along with the appearance of aero-turbine in the forties in 20th century, can under high temperature oxidation atmosphere and exhaust gas corrosion condition, bear bigger working load for a long time, being mainly used in the hot-end component of internal combustion turbine, is the important structure material of aerospace, naval vessel, generating, petrochemical complex and communications and transportation industry.Wherein some alloy also can be used for biotechnology and makes orthopaedics and dental material.

Superalloy commonly used comprises tungsten base, iron-based and cobalt base alloy, can work under 600～1100 ℃ of hot environments; Heat-resisting aluminium alloy then is to grow up during the cold war.The heat-resistance high-strength aluminium alloy is suitable for bearing bigger working load in the thermal environment midium or long term below 400 ℃, is more and more used in fields such as aerospace, heavy industry machineries.Except aero-turbine, internal combustion turbine etc. directly with parts that high-temperature fuel gas contacts, all the other High Temperature High Pressure strong power parts all can adopt the heat-resistance high-strength aluminium alloy casting.

Because the aluminium alloy ratio is easier to processing, along with the raising of processing technology level, under the situation that intensity meets the demands, people adopt wrought aluminium alloy to substitute cast aluminium alloy more and more.Therefore the heat-resistance high-strength aluminium alloy is divided into Ajax alloy and distortion alloy two big classes again.

In general, the heat-resistance high-strength alloy all contains multiple alloy element, many reach ten surplus kind.The element that adds plays effects such as solution strengthening, dispersion-strengthened, grain-boundary strengthening and surface stabilization respectively in alloy, make alloy can at high temperature keep high mechanical property and environmental performance.

The factor that should consider when selecting casting with superalloy for use:

(1) normal working temperature of foundry goods, the highest and minimum working temperature and the frequency of temperature variation.

(2) expansion character of the temperature range of foundry goods itself and alloy.

(3) load performance that bears of foundry goods, loading, supporting and external constraint mode.

(4) to life requirements and the deflection of allowing, Working environment and character, manufacturing process and the cost factor etc. of foundry goods.

Be used for the aluminum alloy materials of high temperature component casting at present, have only A201.0, ZL206, ZL207, ZL208,206.0 several trades mark in the national standard, comprise aluminum bronze Mn series alloy and aluminium rare earth-based alloy; Wherein, aluminum bronze Mn series alloy majority is alloy material with high-purity grade of aluminium ingot, and cost is higher, and then at room temperature mechanical property is relatively poor relatively for the aluminium rare earth-based alloy.And, at present heat-resistance high-strength aluminium alloy ubiquity hot strength low (instantaneous tensile strength is less than 200Mpa more than 250 ℃, creep rupture strength is less than 100Mpa), formulation cost height, defectives such as castability is poor, casting qualified rate is low, waste product material and slag charge reuse difference, problem such as cause that casting quality is poor, cost height, slag charge treatment scheme are long.In addition, also all contain noble element in the new prescription of most heat-resisting aluminium alloy patents of declaring in recent years, and castability is poor, quality can't satisfy the requirement of aeronautical technology progress, is unsuitable for the industrialization production application.

And the heat-resistance high-strength wrought aluminium alloy that in national economy and the modernization of national defense and development, has extensive use and the bright prospect of aurora, report is less in the domestic and foreign literature, known 2219,2A02,2A04,2A06,2A10,2A11,2A12,2A14,2A16,2A17,2A50,2A70,2XXX such as 2A80 are that 7XXX such as wrought aluminium alloy and 7A04 are wrought aluminium alloy, the intensity majority is less than 100Mpa under temperature more than 250 ℃, and its main alloy element is except Cu, outside the Mn, all be with Si, Mg, Zn is as main micro alloying element, and do not add this several elements, and more than 250 ℃ under the temperature heat-resistance high-strength wrought aluminium alloy material of intensity more than 150Mpa be not reported.

3, the rotten processing of aluminium alloy

The high materialization processing of melt is the core link of aluminium alloy smelting and pursues one's goal, is basis and the prerequisite that obtains the fine aluminum alloy material simultaneously.High materialization is handled and is mainly comprised two aspects: the one, and pureization, the 2nd, structural unit refinement and homogenizing.The former takes the method for an impurity solid state filtering and " with the gas degasification " to reduce melt impurity and hydrogen richness, and technological process can produce waste residue and waste gas; The latter is commonly referred to rotten the processing, be with additive or machinery, physical method make the size of the elementary cell--xln--that constitutes aluminium alloy melt and sosoloid become as far as possible little, distribute even as far as possible, because additive enters alloy melt, become the effective ingredient of alloy, thereby do not produce waste residue and waste gas in the process.It is the fundamental means of adjusting the aluminium alloy as-cast structure that efficient alterant is particularly used in rotten processing.

According to the melt crystallization theory, the additive that adds as alterant should satisfy following requirement:

(1) at high temperature chemical ingredients is constant, and enough stability is arranged in molten aluminium;

(2) fusing point of additive should be than the height of aluminium;

(3) lattice of additive and aluminium should adapt on scantlings of the structure;

(4) form powerful adsorption bond with processed melt atom.

Generally adopt the processing of going bad of wire rod or pie additive at present in wrought aluminium alloy material field, comprise titanium, boron, rare earth compound alterant etc., facts have proved, adopt suitable alterant that the performance of wrought aluminium alloy material is had good improvement effect.And in the cast aluminium alloy field, the alterant that adopts mostly is pulverous alkali metal halide composite salt, this type of alterant exist modification effect limited, increase foreign matter content in the aluminium alloy, produce shortcomings such as a large amount of obnoxious flavoures, in melt treatment, realize having increased trace elements again in the whole cleaning action, improved the environmental protection cost simultaneously.Usually, the alkali metal halide composite salt is that the alterant of cast aluminium alloy has modification effect preferably as Al-Si, but is the alterant of alloy as Al-Cu, and modification effect is not enough.

In sum, the problem that exists in the research of heat-resistance high-strength degree field of aluminum alloys both at home and abroad at present has as can be known: lack rotten processing the efficiently in the fusion process, hot strength and weather resistance deficiency, the high temperature instantaneous strength is all less than 250Mpa more than 250 ℃, and creep rupture strength is all less than 100Mpa; The materials processing poor performance; Waste disposal long flow path, cost height can't satisfy the requirement of aeronautical technology progress etc.

Summary of the invention

Technical problem to be solved by this invention is, the melt treatment that exists at present aldural field is extensive, of poor quality, hot cracking tendency is big, castability is poor, the goods yield rate is low, hot strength is low, technical barriers such as waste product material and slag charge reuse difference, with the high-quality melt, sosoloid and phase diagram theory are for instructing, with the C element as efficient alterant, by preferred alloy principal element Cu, Mn and rare earth element prescription, reduce the accurate solid-state temperature scope of alloy, hot cracking tendency is big when solving casting, the problem that is ubiquitous of goods hot strength low (comprising instantaneous strength and creep rupture strength); Preferred low-cost multicomponent microalloying element formula is for material base condition is created in cultivation and the grain refining effect of high temperature phase and strengthening phase in the sosoloid; And optimize melting, thermal treatment process technology, realize high temperature phase and the enough culture of strengthening phase and giving full play to of grain refining effect in the sosoloid.The AlCu that finally develops a kind of rare earth multicomponent micro-alloying is novel high-strength heat-resisting (castibility and deformability) aluminum alloy materials.

Technical scheme of the present invention is, by weight percentage, this alloying constituent is Cu:1.0～10.0%, Mn:0.05～1.5%, Cd:0.01～0.5%, Ti:0.01～0.5%, C:0.0001～0.15%, Zr:0.01～1.0%, Ag:0.01～1.0%, Nb:0.01～1.0%, rare earth elements RE: 0.05～5%, all the other are Al.

Rare earth elements RE is single rare earth element or more than one mixed rare-earth elements.

Rare earth elements RE comprises La, Ce, Pr, Nd, Er and Y.

Should comprise the steps: with the rotten Ag-Nb-RE high strength heat resistant alloy preparation methods of C

(1) in above-mentioned element ratio scope, selected one group of feasible element ratio, again as required the preparation the alloy total amount, extrapolate the quality of every kind of required elemental metals, the perhaps quality of master alloy, perhaps the quality of hybrid metal additive (comprising salt compounds) is worked out the alloy production allocation sheet, and gets the raw materials ready by allocation sheet choosing foot.

(2) add an amount of aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Mn, Ti, Zr, Ag, Nb pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Ag, Al-Nb master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive (comprising salt compounds) after stirring again, add C and rare earth elements RE again, stir.

Wherein, the hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used.Sintered metal product comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix; Flux refers to that the mixture of basic metal or alkaline-earth metal halogen salt is (as NaCl, KCl, Na3AlF ₆Deng).C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) in order to prevent the material burning, determine foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

Compared with prior art, the present invention has following major advantage:

To adopt refined aluminium mostly be matrix material and add noble element to have solved present Al-Cu and be high tough aluminium alloy (ZL201A, ZL 204A, ZL 205A etc.), cost is higher, causing Al-Cu is that high tough aluminium alloy can only be used for leading-edge fields such as aerospace, defence and military, and civil area is used limited problem because cost performance is not high.

Along with the continuous expansion in China of China and the quick growth of world aluminum output and aluminium industry size, " with aluminium for steel " day by day becomes trend and the trend of industry development, and also presses for the high high tough aluminium alloy of cost performance at civil area; The present invention is matrix material by adopting general aluminium, join and give a small amount of noble element, preferred feature micro alloying element prescription, and adopt technologies such as intensive, terse founding, purification, add efficient alterant, develop the novel high-strength heat-resistant aluminium alloy material, overcome the threshold on cost of current material.

Particularly, the present invention has following eight advantages.

1, high strength and high rigidity.From the strength of materials, require under the prerequisite satisfying plasticity, can be by Technology means such as thermal treatments, make various strengthening phases in as-cast structure fully, evenly, rationally separate out and distribute, make the strength of materials reach 480～540Mpa; Hardness 〉=HB140.

2, the double attribute of material.From the material applications attribute, it belongs to the both sexes aluminium alloy, the characteristic of existing cast aluminium alloy has the characteristic of wrought aluminium alloy again, both can be directly used in casting all kinds of light powerful spares and structural part, also can cast bar earlier and be hot extruded into section bar into various sections again.

In essence, this material belongs to the cast aluminium alloy of multicomponent microalloying, but because material has excellent flowing and intergranular self-lubricating property, makes it possess the easy processing characteristics of wrought aluminium alloy simultaneously.

3, the advance of technology.On production technique, changed traditional extensive technology at smelting technique, can use electric furnace to carry out tight protectiveness melting, thereby avoid melt to sneak into too much impurity and gas, complicated follow-up melt treatment flow process has also been simplified and shortened to the purity that had both kept alloy; Simultaneously, fusion process has improved energy utilization rate greatly than the conventional reflective melting technology and has reduced pollution to environment, belongs to environment protecting and power-saving type technology.

(1) the protectiveness melting has significantly reduced energy consumption, pollution, has simplified Production Flow Chart, has improved intensive degree

Because aluminium and aluminium alloy melt have extremely strong air-breathing tendency, so in the bad stove of open type or closure, melt and during melting, the alloy liquid of fusion can absorb airborne O in large quantities ₂, gas such as moisture, generate insoluble Al ₂O ₃With the H with excellent activity ₂, in melt, form impurity and gas, if untimely removing can form the slag inclusion, pore of foundry goods, defective such as loose when casting, cause goods to be scrapped; Wherein especially with H in the melt ₂The harm maximum because H ₂Solubleness when aluminium and aluminium alloy molten state is much higher than the solubleness when solid-state, therefore when solidifying, has a large amount of H ₂From alloy, overflow and cause a large amount of defectives.Insoluble slag is then relatively more easily removed.Therefore, avoiding melt air-breathing is the important measures that keep melt quality and castability.

Common large scale industry aluminium alloy smelting stove is to be reflector oven or the holding furnace of the energy with liquid or geseous fuel, needs a large amount of air-breathings, contains a large amount of water vapors and CO in the products of combustion simultaneously ₂, NO _XDeng material, at high temperature very easily generate various detrimental impurity with aluminium generation chemical reaction, simultaneously the same H that very easily adsorbs with aluminium liquid of these impurity itself ₂, make melt be subjected to severe contamination, before casting, melt must experience together or the special cleaning section in a few road, and the casting flow process of being allowed for access after the sampling detection is qualified, and this has prolonged work flow undoubtedly, and energy consumption and contamination index all are difficult to reduce; Because the continuity requirement of producing must make equipment maximize, increase investment simultaneously, improved the technology access threshold; And the overhaul cost of equipment, start-up cost are all along with maximization and the long flow process of equipment form doubly growth.

And general aluminium alloy casting spare production plant, because production scale is little, equipment is simply extensive, and aluminium alloy melt is seldom taked airtight sfgd., causes melt quality and castability not high equally.

The preparation method that the present invention requires, its melting mode is to adopt the Induction Heating Equipment of with closure, air, water vapor and various products of combustion are to the pollution of melt when having eradicated fuel combustion, simultaneously in fusion process, can adopt protective gas to carry out the protective atmosphere melting, farthest the invasion and attack of secluding air; Owing to kept the high purity of melt, can take very simple through type degasification, deslagging device in cast sections thereafter, and needn't add special stop formula soaking equipment, thereby simplify technical process greatly.

(2) optimize the thermal treatment process of foundry goods, avoided the generation that material mechanical performance reduces, goods are scrapped that causes because of " burning "

Application number is 200810302670.3; 200810302668.6; 200810302669.0 and 4 patent names of 200810302671.8 are in the invention of " a kind of high-strength cast aluminium alloy material "; the heat treatment process parameter of prescribed material is " below 620 ℃; in 72 hours "; in the material application test; when temperature surpasses 560 ℃ when finding solution treatment; " burning " phenomenon usually can take place; cause the destruction of material microstructure; its characteristic feature is that leading indicators such as intensity and ductility significantly reduce; foundry goods becomes fragile; the surface blackening obfuscation, even in heat treatment process, namely crack; the distortion and scrap.And when solid solubility temperature was lower than 470 ℃, because cultivation, the precipitation strength effect of strengthening phase are insufficient, the intensity of material was difficult to reach the desired destination value; Simultaneously, through after test of many times gropes, find that heat treatment time surpasses 30 hours, the raising of material property is not had unusual effect.Therefore, in order to improve effect and efficient, with heat treatment process parameter optimize and revise into: 470～560 ℃, 30 hours with interior solution treatment.

4, Pei Fang science and economy.From raw material sources, the matrix alloy of novel material series can adopt general industry fine aluminium (i.e. two zero aluminium, comprise aluminium liquid and remelting aluminium ingot), must adopt refined aluminium or the high-purity grade of prescription model that aluminium is matrix alloy than existing aldural, have advantages such as raw material supply abundance, cost is low, buying is convenient; Simultaneously, this material can adopt refined aluminium or high-purity grade of aluminium as matrix alloy equally, and the material of this prescription has higher ductility than the general alumina-base material of this kind.

The present invention is the polynary prescription of feature micro alloying element by preferred alloy principal element copper (Cu), manganese (Mn) with silver (Ag), niobium (Nb), for material base condition is created in cultivation and the grain refining effect of high temperature phase and strengthening phase in the sosoloid; Be the efficient alterant of alloy with carbon (C), because the lattice parameter of the carbide that forms is close to the lattice parameter of aluminium sosoloid, these carbide particles group is as crystallization nuclei very tiny (its size is less than 1 μ m) and can stable existence in aluminium liquid under suitable refining temperature, in the ingot solidification process, α-Al had fabulous stable refinement nucleation ability substantially, thereby be better than other alterants with carbon as its antidamping ability of alterant, at utmost improve the alloy organizing dispersity, realize best modification effect; Select for use high temperature elemental niobium (Nb) and silver (Ag), rare earth elements RE as the trace additives of complex alloysization, Nb forms AlNb in alloy ₃～Al ₁₂13 kinds of metallic compound dispersivitys such as Nb High-Temperature Strengthening phase, the hot strength of raising alloy; After adding a small amount of Ag element in the alloy, promoted the formation of timeliness transition phase, improved the stability of GP district and transition phase, improved the alloy aging hardening characteristics, made alloy mechanical property obtain bigger raising; Rare earth (RE) forms multiple metallic compound dispersivity strengthening phase in alloy (for example: Rare-Earth Ce forms α-Ce in alloy ₃Al ₁₁～β-Ce ₃7 kinds of metallic compounds such as Al; Rare earth La forms α-Al in alloy ₁₁La ₃～β l ₁₁La ₃Deng 6 kinds of metallic compounds; Rare earth Pr forms α-Al in alloy ₁₁Pr ₃～β-Al ₁₁Pr ₃Deng 6 kinds of metallic compounds; Rare earth Nd forms α-Al in alloy ₁₁Nd ₃～β-Al ₁₁Nd ₃Deng 6 kinds of metallic compounds; Rare earth Er forms ErAl in alloy ₃, ErAl ₂, ErAl, Er ₃Al ₂, Er ₂5 kinds of metallic compounds such as Al; Rare Earth Y forms Al in alloy ₃Y, Al ₂Y, AlY, Al ₂Y ₃, AlY ₂Deng 5 kinds of metallic compounds; Rare earth Dy forms α-DyAl in alloy ₃～β-DyAl ₃Deng 6 kinds of metallic compounds; Rare earth Eu forms EuAl in alloy ₄, EuAl ₂, 3 kinds of metallic compounds such as EuAl; Rare-earth Sm forms Al in alloy ₁₁Sm ₃, Al ₃Sm, Al ₂Sm, AlSm, AlSm ₂Deng 5 kinds of metallic compounds; Rare earth Pm forms Al in alloy ₁₁Pm ₃, AlPm ₂Deng 5 kinds of infusibility active metallic compounds; Rare-earth Gd forms Al in alloy ₄Gd, Al ₁₇Gd ₂Deng 7 kinds of infusibility active metallic compounds; Rare earth Tb forms Al in alloy ₃Tb, AlTb ₂Deng 5 kinds of infusibility active metallic compounds; Rare earth Ho forms Al in alloy ₃Ho, AlHo ₂Deng 5 kinds of infusibility active metallic compounds; Rare earth Tm forms Al in alloy ₃3 kinds of infusibility active metallic compounds such as Tm, AlTm; Rare Earth Y b forms Al in alloy ₃Yb, Al ₂2 kinds of infusibility active metallic compounds such as Yb; Rare earth Lu forms Al in alloy ₃Lu, AlLu ₂Deng 5 kinds of infusibility active metallic compounds etc.), all improved alloy at room temperature intensity, high-temperature capability and fluidity of molten.

The main alloying element mechanism of action of the present invention is as follows.

1. this material allows copper (Cu) content in 1～10% scope, is that cast aluminium alloy cupric (Cu) amount is that 3～11% scope is slightly different than Al-Cu, but in theory then has earthshaking innovative significance.

On the one hand, it is 5.65～5.7% o'clock at copper (Cu) content, just in time equal the eutectic solubleness of Cu in the Al-Cu alloy, turn model and the mechanism of action according to " fully solid solution-evenly separate out-grain-boundary strengthening phase-brilliant crack weighting agent (bond, inlay, anti-skidding) " in heat treatment process change, and form more rich Cu strengthening phase (comprising Al ₂Cu, i.e. θ phase), thus the room temperature of aluminium alloy and mechanical behavior under high temperature are all improved greatly, also improved processing characteristics; But because the solubility with temperature of Cu in Al reduces and sharply descends, in the crystallization and freezing process, the degree of supersaturation of Cu in α-Al sosoloid improves fast, on one side α-Al dendrite is grown up, increase the tendency of outside crystal boundary, discharging rich Cu strengthening phase on one side strongly, cause structural stress huge between intracrystalline and crystal boundary, alloy monolithic is in the solidification shrinkage stage simultaneously, string stress and structural stress are superimposed, when the instant actual strength that surpasses alloy, then form thermal crack, therefore in the certain limit of copper (Cu) content≤5.65%, the castability of aluminium alloy is the poorest, the hot cracking tendency maximum.But total trend is that along with the reduction of copper content, the hot cracking tendency of alloy also reduces; When Cu content＜1%, its strengthening phase deficiency, the turn model of strengthening phase and the mechanism of action are difficult to give full play to, separating out and can form more defective between crystal boundary to dissolving in of intracrystalline at crystal boundary when temperature variation, reduce alloy at room temperature and hot strength, so it is Cu content is low excessively, nonsensical concerning simple Al-Cu alloy; If but added more rare earth element (RE) in the alloy, then could play remedying the low excessively special-effect of Cu content.

On the other hand, at Cu content 〉=5.7% o'clock, rich Cu can not all be absorbed by matrix when thermal treatment, then be distributed in crystal boundary with border rich Cu metallic compound form disperse, reduced the concentration difference of the inside and outside Cu particle of α-Al sosoloid, mild α-Al sosoloid dendrite is discharged the intensity of rich Cu phase to crystal boundary in process of setting, has namely reduced structural stress and hot cracking tendency.Obviously, when Cu content 〉=5.7%, rich Cu is more many mutually, and the structural stress of alloy inside and hot cracking tendency are more little during crystallization; Simultaneously, the rich Cu of the thin brilliant disperse of high-melting-point forms active heterogeneous nucleus when melt crystallization, accelerate the melt crystallization reaction but stop nuclei growth, refinement crystal grain, also reduced the alloy hot cracking tendency; And make between the matrix crystal boundary filling fuller; Rich Cu can also form the refractory metal compound with multiple element such as Al, Mn mutually.All these effects, the surface tension of the melt that weakened has significantly reduced melt viscosity, thereby has significantly improved the castability of fluidity of molten and alloy.

When Cu content is in 5.7% left and right sides, after heat treatment, at the matrix crystal boundary more rich Cu phase (dissolving in-precipitated phase) and the less thin brilliant disperse phase of (about 0.5%) Cu based metallization compound are arranged, make the alloy strength under the room temperature state keep higher level, but when being in hot environment, because a large amount of rich Cu dissolve in the matrix mutually again, will cause more intergranular space and defective, this can make the hot strength of alloy significantly descend.Along with Cu content continue to increase, the degree of alloy strength temperature influence reduces, and when disperse phase and precipitated phase were in the equivalent state substantially, it is minimum that the strength of materials is acted upon by temperature changes, and Cu content should be 11～12% in the alloy at this moment.

But when Cu content in the alloy＞10%, the Cu of surplus has preferential crystallization character mutually and forms huge network structure during because of crystallization, alloy viscosity strengthens greatly, surplus replaces the principal element that aluminum substrate becomes crystallization control in crystallisation process, original disperse phase is all shielded the good effect of aluminum substrate phase, so the various performances of alloy decline to a great extent again.

According to the checking of above theoretical basis and practice, determine that the zone of reasonableness of main alloying element Cu content is: 1～10% (wt%).

2. this material improves corrosion stability with manganese (Mn) element, shields impurity F e simultaneously, reduces the deleterious effect of Fe.

MnAl because of manganese (Mn) element and matrix effect generation ₆Have identical current potential with fine aluminium, can improve corrosion stability and the weldability of alloy effectively; While, Mn was as the High-Temperature Strengthening phase, had the effect that improves recrystallization temperature, suppresses the recrystal grain alligatoring, can realize the solution strengthening to alloy, additional reinforcement, raising resistance toheat; Under the grain-refining agent effect, can generate the Al of pelletizing shape with the Fe element ₃(Fe, Mn) effectively eliminated the deleterious effect of the alloy of Fe, so the present invention can allow Fe content at wideer scope (Fe≤0.5%), and the benefit of bringing like this is: realize general aluminium substitution refined aluminium, reduce cost, enlarge raw material sources and material Application Areas.

3. mainly use rare earth RE as basic micro alloying element, and its content range is big, reach as high as 5%, can give full play to degasification, slagging-off, cleaning action, crystal grain thinning and the metamorphism of rare earth element in alloy, mechanical property and the solidity to corrosion effect of raising alloy.

The mechanism of rare earth element degasification, slagging-off, cleaning action is: the rare earth element activity is very strong, and oxygen, hydrogen, sulphur, nitrogen etc. are had stronger avidity, and its deoxidizing capacity surpasses existing the strongest reductor--aluminium, can be content 50 * 10 ^-6Oxygen takes off to 10 * 10 ^-6Below, its desulfidation can be 20 * 10 containing the S amount ^-6Take off to 1～5 * 10 ^-6Therefore, the aluminium alloy that contains rare earth when melting, be easy to aluminium liquid in above-mentioned substance generation chemical reaction, reaction product is insoluble to aluminium and enters in the slag, thereby the gas content in the alloy is reduced, the tendency that makes alloy product produce pore and shrinkage porosite reduces greatly.

Rare earth element can significantly improve the mechanical property of alloy.Rare earth element can form stable high melting point metal compound such as Al in aluminium alloy ₄RE, Al ₈CuRE, Al ₈Mn ₄RE, Al ₂₄RE ₃Mn etc.These high melting point metal compound disperses are distributed in intergranular and the interdendritic that is netted or skeleton shape, and with the matrix mortise, played and strengthened and the effect of stable crystal boundary.Simultaneously, also form the AlSiPE phase of some amount in the alloy, because its fusing point and hardness are very high, therefore thermotolerance and the wear resistance that improves alloy all had good effect.In addition, also can in and low melting point impurity element Sn, Pb, Sb etc. in the molten metal, form dystectic compound with them or they evenly distributed in from the interdendritic to whole crystal, eliminated dendritic structure.

Rare earth element has crystal grain thinning and metamorphism.Rare earth element is surface active element, can concentrate to be distributed on the crystal boundary face, reduces melt viscosity, strengthens flowability, reduces pulling force between phase and phase, because the merit that forms the critical size nucleus is reduced, nuclei of crystallization quantity increases, thereby makes grain refining.Rare earth has long-lasting and remelting stability to the metamorphism of aluminium alloy, and most ofs single or mishmetals add then has very strong refinement and metamorphism mutually to α-Al.

In addition, rare earth element can also improve the electroconductibility of alloy.Because rare earth energy refinement aluminium grain also can form stable compound (as CeFe by impurity such as Fe, Si in alloy ₅, CeSi, CeSi ₂Deng) and separate out from intracrystalline, add rare earth to the cleaning action of alloy, make the resistivity of aluminium be reduced, electroconductibility improves (about 2%).

Very a spot of rare earth elements RE can produce significantly rotten improving effect to alloy property, therefore, the rare earth adding quantity of general aluminium alloy is below 1%, in 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 patent applications, content of rare earth is defined as 0.05～0.3%.Analyze from the Al-RE alloy phase diagram, because the solubleness of most of rare earth in aluminium very little (being about 0.01% as Ce), it exists, and form is many to be distributed in crystal boundary or basic intracrystalline portion with high melting point metal compound.Because activity is very high, in cleaning molten, serve as scavenging agent and consume a part, if add-on is very little, then its metamorphism to α-Al phase just is difficult to give full play to.Be the metamorphic long-lasting and remelting stability of maintenance rare earth, and give full play to its High-Temperature Strengthening characteristic, the present invention is special to be considered copper content with content of rare earth, determine that its content range is 0.05～5%.

4. niobium (Nb) element adds element as the feature of complex alloysization, and Nb forms AlNb in alloy ₃～Al ₁₂13 kinds of metallic compound dispersivitys such as Nb High-Temperature Strengthening phase, the hot strength of raising alloy; Silver (Ag) element adds element as the feature of complex alloysization, after adding a small amount of Ag element in the alloy, promote the formation of timeliness transition phase, improved the stability of GP district and transition phase, improved the alloy aging hardening characteristics, made alloy mechanical property obtain bigger raising.

5. be the efficient alterant of alloy with carbon (C), because the lattice parameter of the carbide that forms is close to the lattice parameter of aluminium sosoloid, these carbide particles group is as crystallization nuclei very tiny (its size is less than 1 μ m) and can stable existence in aluminium liquid under suitable refining temperature, in the ingot solidification process, α-Al had fabulous stable refinement nucleation ability substantially, thereby be better than other alterants with carbon as its antidamping ability of alterant, at utmost improve the alloy organizing dispersity, realize best modification effect.

5, You Yi castability.By the foundry goods that uses at several fields such as high-tech structure, Aeronautics and Astronautics, civilian heavy industrys foundry trial repeatedly, verified the excellent properties of this novel material: castability is higher than present A201.0, ZL206, ZL207, ZL208, high strength cast aluminium alloys such as 206.0, the significant problem that hot cracking tendency is big when having solved above-mentioned aluminium alloy casting, casting qualified rate is low; The present invention can be melted down remelting by old material, also can realize the arbitrary proportion batching with virgin material, and new and old material mixed melt casting performance does not have change, and the good action that stable material intensity, raising ductility are arranged, the situation that existing aldural waste material reuse is poor, circulation route is long has utmost point remarkable economical and intensivism.

The principle that novel material is eliminated hot cracking tendency is: form rich Cu phase because copper content in the alloy increases, rich Cu is distributed in crystal boundary as the thin brilliant disperse phase of high-melting-point with the disperse of metallic compound form, the strong tendency that spreads to crystal boundary of having offset effectively when melt crystallization that the rich Cu solute of intragranular forms because degree of supersaturation sharply raises, thereby the structural stress when having slowed down crystallization; The multiple disperse phase of rich Cu disperse phase and Ag, Nb feature micro alloying element, RE microalloying of rare earth element and Mn, Zr, elements such as Ti, C on the while crystal boundary, the multiple effect that all has crystal grain thinning, filling matrix crystal boundary, the nearly aluminium current potential metallic compound of formation, all these act on the surface tension of the melt that weakened significantly, reduced melt viscosity, thereby significantly improved the castability of fluidity of molten and alloy, made cast article have higher qualification rate.

The good principle of old material reuse is: the multicomponent microalloying effect has long-lasting and remelting stability among the present invention, during remelting, the structural performance of melt has kept atom bloc framework and the fine crystalline structure of an alloy melt formation, a large amount of active nucleus can be given full play to the effect of cohesion, assimilation microlitic structure in melt, and can keep original flowability.Therefore, the good action of allocating stable material intensity, raising ductility into of old material.

This specific character of old material can be implemented in the instant reuse of production scene fully, no matter is slag charge, processing clout or rejected casting, all can with together melting or directly add in the melt of virgin material.

This specific character of the present invention, 1XXX system and the 2XXX series high strength aluminum alloy materials qualified casting widely applied at present significantly improve, greatly reduce rejection number, therefore do not need big waste product stockyard (in the actual production, very big scrapground ground often will be cooked up in the aluminium alloy casting workshop) in the production scene; Existing a lot of cast aluminium alloys do not possess remelting stability simultaneously, and therefore direct reuse needs group to criticize and focus at the scene, occupies very big manufacturing cost, derives a series of processing links and fruitless labour; And use novel material provided by the invention, all these extra links, cost and fruitless labour all can be saved.

6, You Yi processing, surface anticorrosion handling property.By novel material being processed into the test of the finished parts of different shapes such as axle, ball, pipe, angle section, bolt, testimonial material has fabulous processability, and the surface can reach the fine and clean degree of nearly minute surface degree, and luminous reflectance factor is higher than fine aluminium; Surface oxidation and coated test show that thickness can reach the standard-required grade after the surperficial anodic oxidation, surface color does not have change, and the tack of coating and oxidized surface reaches the standard class of resistance to rupture test fully.

7, You Yi high-temperature behavior.This material has the characteristic of high temperature aluminium alloys, can reach that intensity is higher than more than the 200Mpa under 400 ℃ of conditions, be higher than traditional high temperature (heat-resisting) aluminum alloy materials, this characteristic makes novel material can substitute other each position heat-resistant part material except aircraft engine casket body directly bears the parts of high-temperature fuel gas calcination.(thermotolerance principle referring in the characteristic 4 " science of prescription and economy " about the content of copper-rich phase, rare earth RE, refractory alloy elements A g, Nb etc.).

8, typical original.This series type material is that the applicant develops after obtaining alloying theory innovation breakthrough fast, the checking of material excellent properties is exactly the checking to the new alloy theory simultaneously, therefore and this theoretical breakthrough was not all clearly put down in writing on all documents and materials at present, should the series novel material belongs to primitiveness, basic great innovation in the world.

Innovative point of the present invention

Table one listed with the present invention in one aspect performance and purposes on close 31 kinds of aluminium alloys elementary composition.As can be seen, compare with existing various high copper content wrought aluminium alloies, heat-resistant deforming aluminium alloy, birmastic, the present invention mainly contains following innovative content.

The one, copper (Cu) content allowed band is big, 1～10%; Cooperate with manganese (Mn) element simultaneously and form multiple High-Temperature Strengthening phase.

The 2nd, mainly use rare earth RE as basic micro alloying element, and its content range is big, reach as high as 5%, can give full play to degasification, slagging-off, cleaning action, crystal grain thinning and the metamorphism of rare earth RE in alloy, mechanical property and the solidity to corrosion effect of raising alloy; Rare earth elements RE is all very strong to the avidity of oxygen, sulphur, nitrogen, hydrogen, thereby the effect of its deoxidation, desulfurization, removal hydrogen and nitrogen is all very strong, in addition, RE is surface active element, can concentrate to be distributed on the crystal boundary face, reduce pulling force between phase and phase, because the merit that forms the critical size nucleus is reduced, nuclei of crystallization quantity increases, thereby makes grain refining.

The 3rd, looser to the restriction ratio of ferro element, allow its content maximum can reach 0.5%, this is for to use general aluminium to open up the space as the founding that matrix carries out alloy.

The 4th, do not use low melting point elements such as magnesium, zinc as the material that produces strengthening phase, avoid decomposition and the conversion of material reinforcement phase under the high temperature, thereby significantly improved the hot strength of material.

The 5th, in alloy, form AlNb with Nb ₃～Al1 ₂13 kinds of metallic compound dispersivitys such as Nb High-Temperature Strengthening phase, the hot strength of raising alloy; Silver (Ag) element adds element as the feature of complex alloysization, after adding a small amount of Ag element in the alloy, promote the formation of timeliness transition phase, improved the stability of GP district and transition phase, improved the alloy aging hardening characteristics, made alloy mechanical property obtain bigger raising.Be used in combination titanium (Ti), zirconium (Zr) element as comprehensive grain-refining agent, make alloy material possess all basic substances of premium propertiess such as the heat-resisting and melt high workability of high-strength and high ductility.

The 6th, be the efficient alterant of alloy with carbon (C), because the lattice parameter of the carbide that forms is close to the lattice parameter of aluminium sosoloid, these carbide particles group is as crystallization nuclei very tiny (its size is less than 1 μ m) and can stable existence in aluminium liquid under suitable refining temperature, in the ingot solidification process, α-Al had fabulous stable refinement nucleation ability substantially, thereby be better than other alterants with carbon as its antidamping ability of alterant, at utmost improve the alloy organizing dispersity, realize best modification effect.

More than be the most tangible several aspects in the characteristic formula of the present invention.

The various aluminum alloy chemically compositions that table one is relevant with the present invention

Mechanical property relatively

The applicant compares the present invention with the mechanical property of existing several high tough aluminium alloys, see Table two.

The mechanical property of table two the present invention and several high-toughness casting aluminum alloys

1. institute's column data is 206.0 high-purity alloys, i.e. W (Si)≤0.05%, W (Fe)≤0.10%.S-sand mold casting, J-permanent mold casting, R-investment cast

As can be seen from Table II, tensile strength 480～540MPa of the present invention, hardness obviously is better than the mechanical property of existing high tough aluminium alloy greater than HB140.

High-temperature behavior

The applicant tests the intensity high temperature endurance performance of the present invention under all temps condition, and contrasts with the existing high temperature endurance performance of using heat-resisting aluminium alloy always, sees Table three.

The high temperature endurance performance of table three the present invention and heat-resisting aluminium alloy commonly used

As can be seen from Table III, room temperature strength of the present invention is greater than 450Mpa, and more than 300Mpa, during 300 ℃ of hot strengths, high temperature endurance performance obviously is better than having the high-temperature and durable of heat-resistance high-strength alloy greater than 200Mpa during 250 ℃ of hot strengths.

In sum, the present invention is that the Ag-Nb-RE high strength heat resistant alloy material of efficient alterant has high-tech content and potential high-end applications field with C.

Embodiment

Embodiment 1:Cu-1.0%, feature micro alloying element-Ag, Nb, basic microalloying rare earth element-lanthanum La, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare-earth elements La again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 485Mpa, unit elongation 7.5%.

Embodiment 2:Cu-4.2%, feature micro alloying element-Ag, Nb, basic microalloying rare-earth elements La, Ce mishmetal, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare-earth elements La, Ce mishmetal again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 538Mpa, unit elongation 6.7%.

Embodiment 3:Cu-5.1%, feature micro alloying element-Ag, Nb, basic microalloying rare earth elements europium Eu, efficient alterant element-C

(1) by the good required various alloying elements of following charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare earth elements europium Eu again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 503Mpa, unit elongation 5.1%.

Embodiment 4:Cu-6.01%, feature micro alloying element-Ag, Nb, basic microalloying rare earth element-La, Ce, Pr mishmetal, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare-earth elements La, Ce, Pr mishmetal again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 533Mpa, unit elongation 4.1%

Embodiment 5:Cu-6.5%, feature micro alloying element-Ag, Nb, basic microalloying rare earth element er Er, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare earth element er again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 527Mpa, unit elongation 6.9%.

Embodiment 6:Cu-7%, feature micro alloying element-Ag, Nb, basic microalloying rear earth element nd Nd, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare earth element nd again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 517Mpa, unit elongation 5.3%.

Embodiment 7:Cu-8%, feature micro alloying element-Ag, Nb, basic microalloying rare-earth element cerium Ce, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare earth element ce again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 501Mpa, unit elongation 4.8%.

Embodiment 8:Cu-10%, feature micro alloying element-Ag, Nb, basic microalloying rare earth element yttrium Y, efficient alterant element-C

(1) by the good required various alloying elements of charge calculation table weighing, as follows.

(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.

(3) add Al-Mn, Al-Ti, Al-Ag, Al-Nb, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add C and rare earth element y again, stir.

The hybrid metal additive refers to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, and comprises that manganese, copper, zirconium, silver, niobium or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na ₃AlF ₆C refers to compound or aluminium carbon master alloy, comprises binary master alloy, ternary master alloy and polynary master alloy.

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should be operated in enclosed environment as far as possible simultaneously.

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.

(6) casting (crystallization and freezing in mold).

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

(8) sample index: tensile strength 487Mpa, unit elongation 3.9%.

Claims (4)

1. one kind with the rotten Ag-Nb-RE high strength heat resistant alloy material of C, it is characterized in that: by weight percentage, this alloying constituent is Cu:1.0～10.0%, Mn:0.05～1.5%, Cd:0.01～0.5%, Ti:0.01～0.5%, C:0.0001～0.15%, Zr:0.01～1.0%, Ag:0.01～1.0%, Nb:0.01～1.0%, rare earth elements RE: 0.05～5%, all the other are Al.

2. according to claim 1 with the rotten Ag-Nb-RE high strength heat resistant alloy material of C, it is characterized in that: rare earth elements RE is single rare earth element or mixed rare-earth elements.

3. an Ag-Nb-RE high strength heat resistant alloy preparation methods that goes bad with C as claimed in claim 2 is characterized in that: comprise the steps:

(1) in above-mentioned element ratio scope, a selected group element ratio, the alloy total amount of preparation is as required again extrapolated the quality of every kind of required elemental metals, the perhaps quality of master alloy, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;

(2) add an amount of aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; Melting process is finished in enclosed environment;

(3) press formula rate again and add Mn, Ti, Zr, Ag, Nb pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Ag, Al-Nb master alloy earlier, add Cu, Cd pure metal or Al-Cu, Al-Cd master alloy after stirring again, add C and rare earth elements RE again, stir;

(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, the melt refining is operated in enclosed environment;

(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled;

(6) casting;

(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.

4. the rotten Ag-Nb-RE high strength heat resistant alloy preparation methods of C according to claim 3, it is characterized in that: in step (4), refining agent refers to chlorine, hexachloroethane or Manganous chloride tetrahydrate.