CN102021408B - Ag-Be-RE aluminium alloy material with high strength and heat resistance and preparation method thereof - Google Patents

Ag-Be-RE aluminium alloy material with high strength and heat resistance and preparation method thereof Download PDF

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CN102021408B
CN102021408B CN 200910307221 CN200910307221A CN102021408B CN 102021408 B CN102021408 B CN 102021408B CN 200910307221 CN200910307221 CN 200910307221 CN 200910307221 A CN200910307221 A CN 200910307221A CN 102021408 B CN102021408 B CN 102021408B
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melt
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aluminium
rare earth
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张中可
车云
陈新孟
门三泉
李祥
胥光酉
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Guizhou Huake Aluminium Material Engineering Technology Research Co Ltd
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Guizhou Huake Aluminium Material Engineering Technology Research Co Ltd
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Abstract

The invention discloses an Ag-Be-RE aluminium alloy material with high strength and heat resistance and a preparation method thereof. The Ag-Be-RE aluminium alloy material comprises the following ingredients in percentage by weight: 1.0-10.0% of Cu, 0.05-1.5% of Mn, 0.01-0.5% of Cd, 0.01-0.5% of Ti, 0.01-0.2% of B, 0.01-1.0% of Zr, 0.01-1.0% of Ag, 0.001-0.1% of Be, 0.05-5% of RE and the balance of A1. In the invention, superior melt, solid solution and phase diagram theories as guidance. A formula of alloy main elements Cu, Mn and RE is preferably selected to reduce the temperature range of alloy quasi solid phases and solve the problems of large heat crack tendency during casting, low product high-temperature strength and the like; and a formula of multielement micro-alloying elements is preferably selected, basic material conditions are provided for the culture and grain refinement action of high-temperature phases and strengthening phases in the solid solution, and the aluminium alloy material with high strength and heat resistance is finally developed.

Description

Ag-Be-RE high strength heat resistant alloy material and preparation method thereof
Technical field
The present invention relates to a kind of aluminum alloy materials and preparation method thereof, particularly Ag-Be-RE high strength heat resistant alloy material 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 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 the each department of national economies 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 again common aluminum alloy and high temperature (or heat-resisting) aluminium alloy.Up to the present, can satisfy the high strength at high temperature needs, only have 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 or be out of shape all belongs to 2 line aluminium alloys; And can satisfy simultaneously the high-temp and high-strength aluminium alloy that good casting property is carried out deformation processing easily, 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 most between 200Mpa~300Mpa, a few trade mark that only has 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 slightly inferior and is made its range of application be subject to larger 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, the process equipment mould is required height, operation is many, so the wrought aluminium alloy production cycle is long, cost is very high.Compare the plurality of advantages such as that cast aluminium alloy has is cheap, organize isotropy, can obtain special tissue, be easy to produce complex-shaped part, can small serial production also can produce in enormous quantities with wrought aluminium alloy.Therefore, develop can the Substitute For Partial wrought aluminium alloy high-toughness casting aluminum alloy material and casting forming process thereof, can reach the purpose of casting and forging, shortening manufacturing cycle, reduction manufacturing cost, have important theory significance and great actual application value.
In the evolution of high-toughness casting aluminum alloy, the A-U5GT that succeeds in developing in 20 beginnings of the century of France occupies an important position, at present representative high-toughness casting aluminum alloy its history at most, be most widely used.China does not have the trade mark corresponding with it at present.
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; The ZL205A alloying constituent is complicated, 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 at present existing registration trade mark 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 large, and because formulation cost is high, range of application is little simultaneously.
Above-mentioned 3 kinds of high-toughness casting aluminum alloys belong to Al-Cu system.This series alloy intensity is high, and plasticity and toughness are also better.But castability is relatively poor, is embodied in that hot cracking tendency is large, 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.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 that is comprised of Cu, Mn, Ti, Cr, Cd, Zr, B and rare earth element, this aluminum alloy materials has 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 large 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 large 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 only have 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 only having 2A16,2A17, these 4 trades mark of 2A20,2B16 more than 6%.All contain the compositions such as more Si, Mg, Zn in these wrought aluminium alloy prescriptions, and do not have 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 again heat-resistance high-strength alloy, the strong alloy of heat or superalloy, 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 for a long time larger working load, 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.
That superalloy commonly used comprises is Ni-based, 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 larger 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, in 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 again Ajax alloy and distortion alloy two large classes.
In general, the heat-resistance high-strength alloy all contains multiple alloy element, many reach more than ten and plants.The element that adds plays respectively the effects such as solution strengthening, dispersion-strengthened, grain-boundary strengthening and surface stabilization 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:
(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 at present the aluminum alloy materials of high temperature component casting, only have 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 take high-purity grade of aluminium ingot as alloy material, and cost is higher, and then at room temperature mechanical property is relatively relatively poor 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), the defective such as formulation cost is high, castability is poor, casting qualified rate is low, waste product material and slag charge reuse are poor, cause the problems such as casting quality is poor, cost is high, the slag charge treatment scheme is 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, the 2XXX such as 2A80 are that the 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.
In sum, the problem that exists in the research of heat-resistant high-strength field of aluminum alloys both at home and abroad at present as can be known has: hot strength and weather resistance are not enough, and high-temperature instantaneous intensity 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 for present aldural field is extensive, of poor quality, hot cracking tendency is large, castability is poor, the goods yield rate is low, hot strength is low, the technical barriers such as waste product material and slag charge reuse are poor, with the high-quality melt, sosoloid and phase diagram theory are for instructing, 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 large when solving casting, the problem that is ubiquitous of goods hot strength low (comprising instantaneous strength and creep rupture strength); Preferred multicomponent microalloying element formula is for material base condition is created in cultivation and the grain refining effect of high-temperature-phase in the sosoloid and strengthening phase; 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.Finally develop a kind of Ag-Be-RE high strength heat resistant alloy material and preparation method thereof.
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%, B:0.01~0.2%, Zr:0.01~1.0%, Be:0.001~0.1%, Ag:0.01~1.0%, rare earth elements RE: 0.05~5%, all the other are Al.
Above-mentioned rare earth elements RE is Rare Earth Elements Determination or more than one mixed rare-earth elements.
Above-mentioned rare earth elements RE comprises La, Ce, Pr, Nd, Er and Y.
The preparation method of this novel high-strength heat-resisting aluminium alloy comprises the steps:
(1) in above-mentioned element ratio scope, selected one group of feasible element ratio, the alloy total amount of preparing as required again, 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 insulation under 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 first Mn, Ti, Zr, Be, Ag pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Be, Al-Ag master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive (comprising salt compounds) after stirring, add again B and rare earth elements RE, 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, beryllium, silver, boron or titanium metal powder and flux mix; Flux refers to that the mixture of basic metal or alkaline-earth metal halogen salt is (such as NaCl, KCl, Na 3AlF 6Deng)
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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:
Having solved present Al-Cu and be high tough aluminium alloy (ZL201A, ZL204A, ZL205A etc.), mostly to adopt refined aluminium be matrix material, cost is higher, causing Al-Cu is that high tough aluminium alloy can only be used for the 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 rapid 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 at civil area also in the urgent need to the high high tough aluminium alloy of cost performance; The present invention is matrix material by adopting general aluminium, preferred feature micro alloying element prescription, and adopt the techniques such as intensive, terse founding, purification, and 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 again the characteristic of wrought aluminium alloy, both can be directly used in casting all kinds of light powerful spares and structural part, also can cast first bar 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 fabulous flowability and intergranular self-lubricating property, makes it possess simultaneously the easy processing characteristics of wrought aluminium alloy.
3, the advance of technique.On production technique, changed traditional extensive technique 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 greatly improved energy utilization rate than the conventional reflective melting technology and has reduced pollution to environment, belongs to environment protecting and power-saving type technique.
(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 melt in the bad stove of open type or closure and during melting, the aluminium alloy of melting is the O in the absorbing air in large quantities 2, the gas such as moisture, generate insoluble Al 2O 3With the H2 with excellent activity, in melt, form impurity and gas, if untimely removing can form the slag inclusion, pore of foundry goods, the defective such as loose when casting, cause goods to be scrapped; Wherein especially maximum with the harm of H2 in the melt, because the solubleness of H2 when aluminium and aluminium alloy molten state is much higher than the solubleness when solid-state, therefore when solidifying, has a large amount of H2 and from alloy, overflow and cause a large amount of defectives.Insoluble slag is then relatively easily removed.Therefore, avoiding melt air-breathing is the important measures that keep melt quality and castability.
Common large scale industry aluminum alloy smelting furnace is reflector oven or the holding furnace take liquid or geseous fuel as the energy, 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 subject 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 all are doubled and redoubled along with the maximization of equipment and long flow process.
And general aluminum alloy cast forging piece production plant, because production scale is little, equipment is simply extensive, and aluminium alloy melt is seldom taked airtight sfgd., causes equally melt quality and castability not high.
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 greatly simplify technical process.
(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 occur; cause the destruction of material microstructure; its characteristic feature is that the 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 target value of expectation; 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, science and the economy of prescription.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 the 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 by preferred alloy principal element copper (Cu), manganese (Mn), take beryllium (Be), silver (Ag) as the polynary prescription of feature micro alloying element, create material base condition for cultivation and the grain refining effect of high-temperature-phase in the sosoloid and strengthening phase, alloy forms rich copper strengthening phase at principal element Cu, Mn and (comprising: θ phase Al 2Cu), T phase (Al 12Mn 2Cu) on the basis, select high temperature element beryllium (Be), silver (Ag) and rare earth elements RE as the trace additives of complex alloys, Be forms α, β dispersivity High-Temperature Strengthening phase in alloy, can prevent oxidation, the scaling loss, air-breathing of alloying element, put forward the density of heavy alloyed metallurgical quality and surface film oxide, can make impurity iron (Fe) become a shape by needle-like, the recoil of sand mold casting and model in the time of also can preventing from pouring into a mould; 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 larger raising; Rare earth (RE) forms various metals 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, Al Sm, Al Sm 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 room temperature strength, high-temperature capability and the fluidity of molten of alloy.
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, when copper (Cu) content is 5.65~5.7%, 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 is evenly separated 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, strongly increase the tendency of outside crystal boundary, discharging rich Cu strengthening phase on one side, 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, hot cracking tendency is 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 is not enough, 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, low-alloyed room temperature and hot strength are fallen, so Cu content is excessively low, nonsensical concerning simple Al-Cu alloy; If but added more rare earth element (RE) in the alloy, then could play remedying the excessively low special-effect of Cu content.
On the other hand, when Cu content 〉=5.7%, 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 mutually, and the structural stress of alloy inside and hot cracking tendency are less 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 Hot-Crack Tendency of Alloy; And make between the matrix crystal boundary filling fuller; Rich Cu can also form the refractory metal compound with multiple elements 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 mutually preferential crystallization character 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 simultaneously impurity F e, reduces the deleterious effect of Fe.
MnAl because of manganese (Mn) element and matrix effect generation 6Have identical current potential with fine aluminium, can effectively improve corrosion stability and the weldability of alloy; 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 of alloy, additional reinforcement, raising resistance toheat; Under the grain-refining agent effect, can with the Al of Fe Element generation pelletizing shape 3(Fe, Mn), effectively eliminated the deleterious effect of Fe alloy, so the present invention can allow Fe content at wider scope (Fe≤0.5%), 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 large, 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, propose heavy alloyed mechanical property and solidity to corrosion effect.
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 AlSiRE phase of some amount in the alloy, because its fusing point and hardness are very high, therefore to putting forward heavy alloyed thermotolerance and wear resistance good effect is arranged all.In addition, also can in and low melting point element Sn, Pb, Sb in the molten metal etc., 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 to the metamorphism of aluminium alloy and remelting stability, and most ofs single or mishmetals add afterwards has very strong refinement and metamorphism mutually to α-Al.
In addition, rare earth element can also be put forward heavy alloyed electroconductibility.Because rare earth energy refinement aluminium grain also can form stable compound (such as CeFe by the impurity such as Fe, Si in alloy 5, CeSi, CeSi 2Deng) and separate out from intracrystalline, add the cleaning action of rare earth alloy, so that the resistivity of aluminium is reduced, electroconductibility improves (about 2%).
Seldom the rare earth elements RE of amount can the alloy performance produce significantly rotten improving effect, 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% such as Ce), it exists form to be distributed in crystal boundary or basic intracrystalline section mainly with high melting point metal compound.Because activity is very high, serves as scavenging agent and consume a part in cleaning molten, if add-on very little, then its metamorphism to α-Al phase just is difficult to give full play to.Be the long-lasting and remelting stability of maintenance RE Modified effect, 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. beryllium (Be) element adds element as the feature of complex alloys, in alloy, can form α, β dispersivity High-Temperature Strengthening phase, can prevent oxidation, the scaling loss, air-breathing of alloying element, put forward the density of heavy alloyed metallurgical quality and surface film oxide, can make impurity iron (Fe) become a shape by needle-like, the recoil of sand mold casting and model in the time of also can preventing from pouring into a mould; Silver (Ag) element adds element as the feature of complex alloys, 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 larger raising.
5, excellent castability.By the foundry goods that uses in the several fields such as high-tech structure, Aeronautics and Astronautics, civilian heavy industry foundry trial repeatedly, verified the excellent properties of this novel material: castability is higher than present A201.0, ZL206, ZL207, ZL208, the high strength cast aluminium alloys such as 206.0, the significant problem that hot cracking tendency is large 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 blend melt casting performance is without 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 extremely significant economy 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, when melt crystallization, effectively offset the strong tendency to the crystal boundary diffusion that rich Cu solute sharply raises and forms because of degree of supersaturation in the crystal grain, thus the structural stress when having slowed down crystallization; The multiple disperse phase of rich Cu disperse phase and Be, Ag feature micro alloying element, RE microalloying of rare earth element and Mn, Zr, the elements such as Ti, B 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 large waste product stockyard (in the actual production, very large 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 large 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, excellent processing, surface anticorrosion handling property.By novel material being processed into the test of the finished parts of the 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 standard-required grade, surface color without change after the surperficial anodic oxidation, and the tack of coating and oxidized surface reaches the standard class of resistance to rupture test fully.
7, excellent 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 element Be, Ag etc.).
8, typical original.This Novel series 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 in the world primitiveness, basic great innovation.
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.Can find out that 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 large, 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 large, 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, propose heavy alloyed mechanical property and solidity to corrosion effect; 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 the 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, add element with beryllium (Be) element as the feature of complex alloys, in alloy, can form α, β dispersivity High-Temperature Strengthening phase, can prevent oxidation, the scaling loss, air-breathing of alloying element, put forward the density of heavy alloyed metallurgical quality and surface film oxide, can make impurity iron (Fe) become a shape by needle-like, the recoil of sand mold casting and model in the time of also can preventing from pouring into a mould; 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 larger raising.Be combined with titanium (Ti), boron (B), 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.
More than be the most obvious five aspects in the characteristic formula of the present invention.
The various aluminum alloy chemical compositions that table one is relevant with the present invention
Mechanical performance compare
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 commonly using heat-resisting aluminium alloy, 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 the high-temperature and durable of existing heat-resistance high-strength alloy greater than 200Mpa during 250 ℃ of hot strengths.
In sum, Ag-Be-RE high strength heat resistant alloy material of the present invention has high-tech content and potential high-end applications field.
Embodiment
Embodiment 1:Cu-1.0%, feature micro alloying element-Be, Ag, basic microalloying rare earth element-lanthanum La
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare-earth elements La, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rare earth element La and Ce mishmetal
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element La and Ce mishmetal, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rare earth element Eu
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element Eu, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rare earth element-La, Ce, Pr mishmetal
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element La and Ce, Pr mishmetal, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rare earth element er Er
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element er, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rear earth element nd Nd
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element nd, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rare-earth element cerium Ce
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element ce, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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-Be, Ag, basic microalloying rare earth element yttrium Y
(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 insulation under 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 first Al-Mn, Al-Ti, Al-Be, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth element y, 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, beryllium, silver, boron 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 6
(4) then above-mentioned alloy melt is carried out furnace refining; Adding refining agent in the alloy melt (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes, and boron salt alterant etc.), and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed.
(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. Ag-Be-RE high strength heat resistant alloy material, 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%, B:0.01~0.2%, Zr:0.01~1.0%, Ag:0.01~1.0%, Be:0.001~0.1%, rare earth elements RE: 0.05~5%, all the other are Al;
Described Ag-Be-RE high strength heat resistant alloy material preparation method comprises the steps:
(1) in above-mentioned element ratio scope, a selected group element ratio, the alloy total amount of preparing as required again, extrapolate the quality of every kind of required elemental metals, the perhaps quality of master alloy, perhaps the quality of hybrid metal additive is worked out the alloy production allocation sheet, and gets the raw materials ready by allocation sheet choosing foot;
Above-mentioned hybrid metal additive, refer to add, adjust pie or the block non-coking property sintered metal product that the alloy constituent element is used, mixed by manganese, copper, zirconium, silver, beryllium, boron or titanium metal powder and flux, wherein flux refers to the mixture of basic metal halogen salt or the mixture of alkaline-earth metal halogen salt;
(2) add an amount of aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and insulation under 700~800 ℃; Melting process is finished in enclosed environment;
(3) add first Mn, Ti, Zr, Ag, Be pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Ag, Al-Be master alloy or hybrid metal additive by formula rate again, add again Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive after stirring, add again B and rare earth elements RE, stir;
(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, the melt refining operates in enclosed environment;
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, online degasification, slagging-off are processed;
(6) casting;
(7) foundry goods is carried out 470~560 ℃, 30 hours with interior solution treatment.
2. Ag-Be-RE high strength heat resistant alloy material according to claim 1, it is characterized in that: rare earth elements RE is Rare Earth Elements Determination or mixed rare-earth elements.
3. Ag-Be-RE high strength heat resistant alloy material according to claim 1 and 2, it is characterized in that: rare earth elements RE comprises La, Ce, Pr, Nd, Er and Y.
4. Ag-Be-RE high strength heat resistant alloy material preparation method according to claim 1, it is characterized in that: in step (4), refining agent refers to chlorine, hexachloroethane, Manganous chloride tetrahydrate and boron salt alterant.
CN 200910307221 2009-09-17 2009-09-17 Ag-Be-RE aluminium alloy material with high strength and heat resistance and preparation method thereof Active CN102021408B (en)

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