CN102021400B - Ag-W-RE high-strength heat-resistance aluminum alloy material and preparation method thereof - Google Patents

Ag-W-RE high-strength heat-resistance aluminum alloy material and preparation method thereof Download PDF

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CN102021400B
CN102021400B CN200910307188.3A CN200910307188A CN102021400B CN 102021400 B CN102021400 B CN 102021400B CN 200910307188 A CN200910307188 A CN 200910307188A CN 102021400 B CN102021400 B CN 102021400B
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alloy
melt
rare earth
aluminium
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CN102021400A (en
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张中可
车云
陈新孟
门三泉
李祥
曹跃清
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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-W-RE high-strength heat-resistance aluminum alloy material and a preparation method thereof. The Ag-W-RE high-strength heat-resistance 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, 0.01 to 0.2 percent of B, 0.01 to 1.0 percent of Zr, 0.01 to 1.0 percent of W, 0.01 to 1.0 percent of Ag, 0.05 to 5 percent of RE and the balance of Al. In the invention, based on high-quality melt, solid solution and phase diagram theories, the problems of large hot cracking tendency low high-temperature strength of products and the like in casting are solved by preferably selecting a formula of alloy main elements including Cu, Mn and RE and reducing the quasi solid phase temperature range of the alloy; and a multivariant microalloying element formula is selected preferably to create material basic condition for culturing and grain refining functions of the high-temperature phase and reinforced phase in solid solution, and finally, a high-strength and heat-resistance aluminum alloy material is developed.

Description

Ag-W-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 a kind of Ag-W-RE high strength heat resistant alloy material and preparation method thereof.
Background technology
Aluminium alloy is a kind of younger metallic substance, in 20 beginnings of the century, just starts industrial application.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, aluminium industry member is just started to develop civil aluminum alloy, make its range of application by aircraft industry, be expanded to the each department of national economies such as construction industry, container package industry, transportation, electric power and electronic industry, machinery manufacturing industry and petrochemical complex, be applied in the middle of 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; The temperature condition that can use from goods is divided, and aldural is divided into again common aluminum alloy and high temperature (or heat-resisting) aluminium alloy.Up to the present, can meet high strength at high temperature needs, only have Al-Cu line aluminium alloy, from trade mark series, Al-Cu is associated gold and 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 meet the high-temp and high-strength aluminium alloy that good casting property is easily carried out deformation processing simultaneously, also do not see open 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 highest with the intensity of AlCu system and AlZn line aluminium alloy, but most between 200Mpa~300Mpa, a few trade mark that only has AlCu system higher than 400Mpa, but because adopting 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 adopt wrought aluminium alloy as extraordinary traction engine bogie wheel, aviation alloyed aluminium etc., rather than cast aluminium alloy.Wrought aluminium alloy has reduced defect by means such as extruding, rolling, forgings, refinement crystal grain, improved density, thereby there is very high intensity, good toughness and good use properties.But high to the requirement of process equipment mould, 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 Substitute For Partial wrought aluminium alloy high-toughness casting aluminum alloy material and casting forming process thereof, the object that can reach casting and forging, shortening manufacturing cycle, reduction manufacturing cost, has important theory significance 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; Behind the US aluminum association trade mark 201.0 (1986) and 206.0 (1967), on A-U5GT basis, transform and form, there is good mechanical property and stress corrosion resistant ability.
In high-toughness casting aluminum alloy field, China has obtained the achievement of attracting attention in the world.The sixties, Beijing Research Inst. of Aeronautic Material succeeded in developing ZL205A alloy to the seventies.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 existing registration trade mark is at present the highest.The obdurability of ZL205A (T5) is best, and unit elongation can reach 13%; But that the defect of ZL205A maximum is castability is poor, hot cracking tendency is large, 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 poor, be embodied in that hot cracking tendency is large, mobility is poor, feeding is difficult.In addition, this series alloy etch resistant properties is poor, has intergranular corrosion tendency.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 being 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 problem, alloy strength and castability that hot cracking tendency is large, its major cause is at alloy principal element Cu, Mn composition range, the accurate solid-state temperature a wider range of alloy, during casting solidification, for thering is anisotropic dendrite growth, provide sufficient condition, 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 more than 5% high X alloy, and wherein copper content more than 6% is only having 2A16,2A17, these 4 trades mark of 2A20,2B16.In these wrought aluminium alloy formulas, all contain the compositions such as more Si, Mg, Zn, and do not have rare earth (RE) etc. to play the element of Microalloying Effect, therefore its formula 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 growing 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.
Conventional superalloy comprises tungsten base, iron-based and tungsten-bast alloy, can under 600~1100 ℃ of hot environments, work; Heat-resisting aluminium alloy is to grow up during cold war.Heat-resistance high-strength aluminium alloy is suitable in the thermal environment below 400 ℃, bearing for a long time larger working load, in fields such as aerospace, heavy industry machineries, is more and more applied.Except the parts that aero-turbine, internal combustion turbine etc. directly contact with high-temperature fuel gas, all the other High Temperature High Pressure strong power parts all can adopt the casting of heat-resistance high-strength aluminium alloy.
Because 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 heat-resistance high-strength aluminium alloy is divided into again Ajax alloy and the large class of alloy two for distortion.
In general, heat-resistance high-strength alloy all contains multiple alloy element, many reach more than ten and plants.The element adding plays respectively the effects such as solution strengthening, dispersion-strengthened, grain-boundary strengthening and surface stabilization in alloy, makes alloy can at high temperature keep high mechanical property and environmental performance.
The factor that should consider while selecting casting with superalloy:
(1) normal working temperature of foundry goods, the highest and minimum working temperature and the frequency of temperature variation.
(2) temperature range of foundry goods itself and the expansion character of alloy.
(3) load performance that foundry goods bears, loading, supporting and external constraint mode.
(4) to the life requirements of foundry goods and the deflection of allowing, Working environment and character, manufacturing process and cost factor etc.
For the aluminum alloy materials of high temperature component casting, in national standard, only have A201.0, ZL206, ZL207, ZL208,206.0 several trades mark at present, comprise aluminum bronze Mn series alloy and aluminium rare earth-based alloy; Wherein, aluminum bronze Mn series alloy majority be take high-purity grade of aluminium ingot as alloy material, and cost is higher, and at room temperature mechanical property is relatively poor for aluminium rare earth-based alloy.And, at present heat-resistance high-strength aluminium alloy ubiquity hot strength low (250 ℃ of above instantaneous tensile strength is less than 200Mpa, creep rupture strength is less than 100Mpa), formulation cost is high, castability is poor, casting qualified rate is low, waste product material and the defect such as slag charge reuse is poor, causes the problems such as casting quality is poor, cost is high, slag charge treatment scheme is long.In addition, also all contain noble element, and castability is poor in the new formula of most heat-resisting aluminium alloy patents of declaring in recent years, quality cannot meet the requirement of aeronautical technology progress, is unsuitable for industrialization production application.
And in national economy and the modernization of national defense and development, there is the heat-resistance high-strength wrought aluminium alloy of extensive use and utmost point the bright outlook, in domestic and foreign literature, report less, 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, at more than 250 ℃ temperature, intensity majority is less than 100Mpa, and its main alloy element is except Cu, outside Mn, all with Si, Mg, Zn is as main micro alloying element, and do not add this several elements, and at 250 ℃ of above temperature, the heat-resistance high-strength wrought aluminium alloy material of intensity more than 150Mpa is not reported.
In sum, the known problem existing in the research of heat-resistant high-strength field of aluminum alloys both at home and abroad at present has: hot strength and weather resistance are not enough, and 250 ℃ of above high-temperature instantaneous intensity are all less than 250Mpa, and creep rupture strength is all less than 100Mpa; Materials processing poor performance; Waste disposal long flow path, cost are high, cannot meet 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 current aldural field is extensive, of poor quality, hot cracking tendency is large, castability is poor, goods yield rate low and high temperature intensity is low, waste product material and the technical barrier such as slag charge reuse is poor, take high-quality melt, sosoloid and phase diagram theory as guidance, by preferred alloy principal element Cu, Mn and rare earth element, fill a prescription, reduce the accurate solid-state temperature scope of alloy, the problem being ubiquitous of large, the goods hot strength low (comprising instantaneous strength and creep rupture strength) of hot cracking tendency while solving casting; Preferably multicomponent microalloying element formula, is cultivation and the grain refining effect creation material base condition of high-temperature-phase in 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 sosoloid.The Al-Cu 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%, B:0.01~0.2%, Zr:0.01~1.0%, W:0.01~1.0%, 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) within the scope of above-mentioned element ratio, 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, or the quality of master alloy, or the quality of hybrid metal additive (comprising salt compounds), establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot.
(2) in smelting furnace, add appropriate aluminium ingot or molten aluminum liquid, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Mn, Ti, Zr, W, Ag pure metal or Al-Mn, Al-Ti, Al-Zr, Al-W, Al-Ag master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive (comprising salt compounds), add again B and rare earth elements RE, stir.
Wherein, hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used.Sintered metal product comprises that manganese, copper, zirconium, tungsten, 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 (as NaCl, KCl, Na 3alF 6deng)
(4) then above-mentioned alloy melt is carried out to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7), in order to prevent material burning, determine foundry goods is carried out to 470~560 ℃, 30 hours with interior solution treatment.
Compared with prior art, the present invention has following major advantage:
Having solved current Al-Cu and be high tough aluminium alloy (ZL201A, ZL 204A, ZL 205A etc.), mostly to adopt refined aluminium be matrix material, cost is higher, causing Al-Cu is that high tough aluminium alloy can only be for leading-edge fields such as aerospace, defence and militaries, and civil area is applied 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 tough aluminium alloy of the high height of cost performance; The present invention is matrix material by adopting general aluminium, preferred feature micro alloying element formula, and adopt the techniques such as intensive, terse founding, purification, and develop 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, meeting under plasticity requirement prerequisite, can make various strengthening phases in as-cast structure, fully, evenly, rationally separate out and distribute by Technology means such as thermal treatments, make the strength of materials reach 480~540MPa; Hardness >=HB140.
2, the double attribute of material.From material applications attribute, it belongs to 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 all kinds of light powerful parts of casting and structural part, also can first cast bar and be hot extruded into the section bar into various sections again.
In essence, this material belongs to the cast aluminium alloy of multicomponent microalloying, but because material has fabulous mobility and intergranular self-lubricating property, makes it possess the easy processing characteristics of wrought aluminium alloy simultaneously.
3, the advance of technique.From production technique, on smelting technique, changed traditional extensive technique, can use electric furnace to carry out tight protectiveness melting, thereby avoid melt to sneak into too much impurity and gas, both the purity that had kept alloy, has also simplified and has shortened complicated follow-up melt treatment flow process; Meanwhile, fusion process has greatly improved energy utilization rate and has reduced the pollution to environment compared with conventional reflective melting technology, belongs to environment protecting and power-saving type technique.
(1) 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, therefore melt in open type or the bad stove of closure and during melting, the aluminium alloy of melting can absorb airborne O in large quantities 2, the gas such as moisture, generate insoluble Al 2o 3with the H with excellent activity 2, in melt, form impurity and gas, if removed not in time, can form the slag inclusion, pore of foundry goods, the defect such as loose in when casting, cause goods to be scrapped; Wherein especially with H in melt 2harm maximum because H 2solubleness when aluminium and aluminium alloy molten state is much higher than solubleness when solid-state, therefore, when solidifying, has a large amount of H 2from alloy, overflow and cause a large amount of defects.Insoluble slag is 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 to take reflector oven or the holding furnace that liquid or geseous fuel be the energy, needs a large amount of air-breathings, contains a large amount of water vapors and W in products of combustion simultaneously 2, NO xdeng material, at high temperature very easily generate various detrimental impurity with aluminium generation chemical reaction, simultaneously these impurity very easily adsorb H the same as aluminium liquid itself 2, make melt be subject to severe contamination, before casting, melt must experience the special cleaning section in Huo Ji road one, and the casting flow process of being allowed for access after sampling detection is qualified, and this has extended work flow undoubtedly, and energy consumption and contamination index are all difficult to reduce; Because the continuity requirement of producing must make equipment maximize, increase investment simultaneously, improved technology access threshold; And the overhaul cost of equipment, start-up cost are all 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 to airtight sfgd., causes equally melt quality and castability not high.
The preparation method that the present invention requires, its melting mode is the Induction Heating Equipment that adopts with closure, air, water vapor and the pollution of various products of combustion to melt while having eradicated fuel combustion, simultaneously in fusion process, can adopt protective gas to carry out protective atmosphere melting, farthest the invasion and attack of isolated air; Owing to having kept the high purity of melt, in cast sections thereafter, can take very simple through type degasification, deslagging device, 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 causing because of " burning "
Application number is 200810302670.3, 200810302668.6, 4 patent names of 200810302669.0 and 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 material application test, when while finding solution treatment, temperature surpasses 560 ℃, usually can there is " burning " phenomenon, 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, surface blackening obfuscation, even in heat treatment process, crack, be out of shape and scrap.And when solid solubility temperature is during lower than 470 ℃, because cultivation, the precipitation strength effect of strengthening phase are insufficient, the intensity of material is difficult to reach the target value of expectation; Meanwhile, after test of many times is groped, find that heat treatment time surpasses 30 hours, does not have unusual effect to the raising of material property.Therefore, in order to improve effect and efficiency, by heat treatment process parameter optimize and revise into: 470~560 ℃, 30 hours with interior solution treatment.
4, science and the economy of formula.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), than existing aldural, must adopt refined aluminium or the high-purity grade of prescription model that aluminium is matrix alloy, there is the advantages such as raw material supply abundance, cost is low, buying is convenient; Meanwhile, this material can adopt refined aluminium or high-purity grade of aluminium as matrix alloy equally, and the material of this formula 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 tungsten (W), silver (Ag) the polynary formula that is feature micro alloying element, for cultivation and the grain refining effect of high-temperature-phase in sosoloid and strengthening phase, create material base condition, alloy forms rich copper strengthening phase at principal element Cu, Mn and (comprising: θ phase Al 2cu), T phase (Al 12mn 2cu) on basis, select high temperature elemental tungsten (W) and silver (Ag), rare earth elements RE as the trace additives of complex alloys, W forms Al in alloy 12w, Al 6w, Al 43 kinds of dispersivity High-Temperature Strengthening phases such as W, put forward heavy alloyed hot strength; In alloy, add after a small amount of Ag element, promoted the formation of timeliness transition phase, improve the stability of LiaoGP district and transition phase, improved alloy aging hardening characteristics, make alloy mechanical property obtain larger raising; Rare earth (RE) (for example: Rare-Earth Ce forms α-Ce in alloy forms various metals compound dispersivity strengthening phase 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 Td 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, but in theory has earthshaking innovative significance compared with Al-Cu.
On the one hand, when copper (Cu) content is 5.65~5.7%, just in time equal the eutectic solubleness of Cu in Al-Cu alloy, in heat treatment process, according to turn model and the mechanism of action of " completely solid solution-evenly separate out-grain-boundary strengthening phase-brilliant gap weighting agent (bond, inlay, anti-skidding) ", change, 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 decline, in 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 discharging rich Cu strengthening phase outside crystal boundary 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 surpassing the instant actual strength of alloy, 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 defect 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 too low, nonsensical concerning simple Al-Cu alloy; If but in alloy, added more rare earth element (RE), could play and make up the too 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, with border rich Cu metallic compound form disperse, be distributed in crystal boundary, reduced the concentration difference of the inside and outside Cu particle of α-Al sosoloid, in process of setting, mild α-Al sosoloid dendrite is discharged the intensity of rich Cu phase to crystal boundary, has reduced structural stress and hot cracking tendency.Obviously, when Cu content >=5.7%, rich Cu is more mutually, and during crystallization, the structural stress of alloy inside and hot cracking tendency are less; Meanwhile, the rich Cu of the thin brilliant disperse of high-melting-point forms active heterogeneous nucleus when melt crystallization, accelerate melt crystallization reaction but stop nuclei growth, refinement crystal grain, also reduced Hot-Crack Tendency of Alloy; And make between matrix crystal boundary filling fuller; Rich Cu can also form refractory metal compound with the multiple element such as Al, Mn mutually.All these act on, and have weakened significantly the surface tension of melt, have reduced melt viscosity, thereby have significantly improved the castability of fluidity of molten and alloy.
When Cu content is during in 5.7% left and right, after heat treatment, at matrix crystal boundary, there are more rich Cu phase (dissolving in-precipitated phase) and the less thin brilliant disperse phase of (approximately 0.5%) Cu based metallization compound, make the alloy strength under room temperature state keep higher level, but when in hot environment, because a large amount of rich Cu dissolve in matrix mutually again, will cause more intergranular space and defect, this can make the hot strength of alloy significantly decline.Along with Cu content continue to increase, the degree of alloy strength temperature influence reduces, and when disperse phase and precipitated phase are during substantially in equivalent state, it is minimum that the strength of materials is acted upon by temperature changes, and now in alloy, Cu content should be 11~12%.
But in alloy during Cu content > 10%, during because of crystallization, the Cu of surplus has mutually preferential crystallization character and forms huge network structure, 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 6there is identical current potential with fine aluminium, can effectively improve corrosion stability and the weldability of alloy; While, Mn was as High-Temperature Strengthening phase, had the effect that improves recrystallization temperature, suppresses recrystal grain alligatoring, can realize the solution strengthening of alloy, supplementary strengthening, raising resistance toheat; Under 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 is like this: realize general aluminium substitution refined aluminium, reduce costs, expand 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: rare earth element activity is very strong, and oxygen, hydrogen, sulphur, nitrogen etc. are had to stronger avidity, and its deoxidizing capacity surpasses the strongest existing reductor--aluminium, can be 50 * 10 content -6oxygen, takes off to 10 * 10 -6below, its desulfidation can be 20 * 10 measuring containing S -6take off to 1~5 * 10 -6.Therefore, containing the aluminium alloy of 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 slag, thereby the gas content in 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 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 matrix mortise, played the effect of strengthening and stable crystal boundary.Meanwhile, in alloy, also form the AlSiRE phase of some amount, due to its fusing point and hardness very high, therefore to putting forward heavy alloyed thermotolerance and wear resistance, all have good effect.In addition, also can in and low melting point element Sn, Pb, Sb in molten metal etc., form dystectic compound with them or they be uniformly distributed in whole crystal from interdendritic, eliminated dendritic structure.
Rare earth element has crystal grain thinning and metamorphism.Rare earth element is surface active element, can concentrate and be distributed on crystal boundary face, reduces melt viscosity, strengthens mobility, reduces pulling force between phase and phase, because the merit that forms 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 of single or mishmetals add has very strong refinement and metamorphism mutually afterwards to α-Al.
In addition, rare earth element can also be put forward heavy alloyed electroconductibility.Due to rare earth energy refinement aluminium grain, also can in alloy, form stable compound (as CeFe by the impurity such as Fe, Si 5, CeSi, CeSi 2deng) and separate out from intracrystalline, add the cleaning action of rare earth alloy, the resistivity of aluminium is reduced, electroconductibility improves (approximately 2%).
Seldom the rare earth elements RE of amount can 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%.From Al-RE alloy phase diagram, analyze, due to the solubleness of most of rare earth in aluminium very little (as Ce is about 0.01%), it exists form to be distributed in crystal boundary or base intracrystalline portion mainly 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, its metamorphism to α-Al phase is just difficult to give full play to.For keeping the long-lasting and remelting stability of RE Modified effect, and give full play to its High-Temperature Strengthening characteristic, the present invention is special to be considered copper content together with content of rare earth, determines that its content range is 0.05~5%.
4. tungsten (W) element adds element as the feature of complex alloys, and W forms Al in alloy 12w, Al 6w, Al 43 kinds of dispersivity High-Temperature Strengthening phases such as W, put forward heavy alloyed hot strength; Silver (Ag) element adds element as the feature of complex alloys, in alloy, add after a small amount of Ag element, promoted the formation of timeliness transition phase, improve the stability of LiaoGP district and transition phase, improved 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 current A201.0, ZL206, ZL207, ZL208, the high strength cast aluminum alloys such as 206.0, the significant problem that while having solved above-mentioned aluminium alloy casting, hot cracking tendency is large, casting qualified rate is low; The present invention can be melted down remelting by old material, also can realize arbitrary proportion batching with virgin material, and new and old material blend melt casting performance is without change, and the good action that has stable material intensity, raising ductility, the situation that the reuse of more existing aldural waste material is poor, circulation route is long, has extremely significant economy and intensivism.
The principle that novel material is eliminated hot cracking tendency is: because copper content in alloy increases, form rich Cu phase, 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 crystal boundary diffusion that in crystal grain, rich Cu solute forms because degree of supersaturation sharply raises, thus the structural stress while having slowed down crystallization; The multiple disperse phase of the element such as rich Cu disperse phase and W, Ag feature micro alloying element, RE microalloying of rare earth element and Mn, Zr, Ti, B on crystal boundary simultaneously, all there is crystal grain thinning, filling matrix crystal boundary, form the multiple effect of nearly aluminium current potential metallic compound, all these effects have weakened the surface tension of melt significantly, reduced melt viscosity, thereby significantly improved the castability of fluidity of molten and alloy, guaranteed that cast article has higher qualification rate.
The good principle of old material reuse is: in the present invention, multicomponent microalloying effect has long-lasting and remelting stability, 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 mobility.Therefore, the good action of allocating stable material intensity, raising ductility into of old material.
This specific character of old material, can realize the instant reuse in production scene completely, is no matter slag charge, processing clout or rejected casting, all can with together melting or directly add in 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 in production scene, do not need large waste product stockyard (in actual production, very large scrapground ground often will be cooked up in aluminium alloy casting workshop); Existing a lot of cast aluminium alloys do not possess remelting stability simultaneously, and direct reuse, therefore needs group batch to focus at the scene, occupies very large manufacturing cost, derives a series of processing links and fruitless labour; And apply 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 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, after surperficial anodic oxidation, thickness can reach standard-required grade, surface color without change, and the tack of coating and oxidized surface reaches the standard class of resistance to rupture test completely.
7, excellent high-temperature behavior.This material has the characteristic of high temperature aluminium alloys, can reach under 400 ℃ of conditions intensity higher than more than 200Mpa, 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 characteristic 4 " science of formula and economy " about the content of copper-rich phase, rare earth RE, refractory alloy element W, Ag etc.).
8, typically original.This Novel series material is that applicant develops fast after obtaining alloying theory innovation breakthrough, the checking of material excellent properties is exactly the checking to new alloy theory simultaneously, and this theoretical breakthrough was not all clearly recorded at present in all documents and materials, so this series novel material belongs to primitiveness, basic great innovation in the world.
Innovative point of the present invention
Table one listed with performance in one aspect of the present invention and purposes on close 31 kinds of aluminium alloys elementary composition.Can find out, 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%; With manganese (Mn) element, coordinate and form multiple High-Temperature Strengthening phase simultaneously.
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 and be distributed on crystal boundary face, reduce pulling force between phase and phase, because the merit that forms 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 using general aluminium to open up space for 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 high temperature, thereby significantly improved the hot strength of material.
The 5th, the W element of usining adds element as the feature of complex alloys, and W forms Al in alloy 12w, Al 6w, Al 43 kinds of dispersivity High-Temperature Strengthening phases such as W, put forward heavy alloyed hot strength; Silver (Ag) element adds element as the feature of complex alloys, in alloy, add after a small amount of Ag element, promoted the formation of timeliness transition phase, improve the stability of LiaoGP district and transition phase, improved 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 the most obvious five aspects in characteristic formula of the present invention.
The various aluminum alloy chemical compositions that table one is relevant with the present invention
Mechanical performance compare
Applicant contrasts the mechanical property of the present invention and existing several high tough aluminium alloys, in 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 is greater than HB140, is obviously better than the mechanical property of the tough aluminium alloy of existing height.
High-temperature behavior
Applicant to the present invention the intensity high temperature endurance performance under all temps condition test, and contrast with the high temperature endurance performance of existing conventional heat-resisting aluminium alloy, in Table three.
The high temperature endurance performance of table three the present invention and conventional heat-resisting aluminium alloy
As can be seen from Table III, room temperature strength of the present invention is greater than 450Mpa, and during 250 ℃ of hot strengths, more than 300Mpa, during 300 ℃ of hot strengths, high temperature endurance performance is greater than 200Mpa, is obviously better than the high-temperature and durable of existing heat-resistance high-strength alloy.
In sum, Ag-W-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-W, Ag, basic microalloying rare earth element-lanthanum La
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare-earth elements La, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rare earth element La and Ce mishmetal
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element La and Ce mishmetal, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rare earth element Eu
(1) by following charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element Eu, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rare earth element-La, Ce, Pr mishmetal
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element La and Ce, Pr mishmetal, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rare earth element er Er
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element er, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rear earth element nd Nd
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element nd, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rare-earth element cerium Ce
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element ce, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 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-W, Ag, basic microalloying rare earth element yttrium Y
(1) by charge calculation table, weighed required various alloying elements, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and insulation at 700~800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) by formula rate, first add Al-Mn, Al-Ti, Al-W, Al-Ag, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) again, after stirring, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive, add again B and rare earth element y, stir.
Hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used, comprises that manganese, copper, zirconium, tungsten, 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 to furnace refining; In alloy melt, add refining agent (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, melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470~560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 487Mpa, unit elongation 3.9%.

Claims (4)

1. an Ag-W-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%, W:0.01~1.0%, Ag:0.01~1.0%, rare earth elements RE: 0.05~5%, Si :≤0.1%, Fe≤0.5%, the single content of other impurity element is not more than 0.05%, and summation is not more than 0.15%, all the other are Al, and this matrix alloy be take general industry fine aluminium as raw material;
Its preparation method, comprises the steps:
(1) within the scope of above-mentioned element ratio, a selected group element ratio, the alloy total amount of preparing as required again, extrapolate the quality of every kind of required elemental metals, or the quality of master alloy, or the quality of hybrid metal additive, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
(2) in smelting furnace, add appropriate aluminium ingot or molten aluminum liquid, heating makes it to melt completely and insulation at 700~800 ℃; Melting process completes in enclosed environment;
(3) by formula rate, first add Mn, Ti, Zr, W, Ag pure metal or Al-Mn, Al-Ti, Al-Zr, Al-W, Al-Ag master alloy again, after stirring, add again Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive, add again B and rare earth elements RE, stir;
(4) then alloy melt carries out furnace refining; In alloy melt, add refining agent, and stir, melt refining operates in enclosed environment;
(5) slag hitting after refining, standing, temperature adjustment to 630~850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed;
(6) casting;
(7) foundry goods is carried out to 470~560 ℃, 30 hours with interior solution treatment.
2. Ag-W-RE high strength heat resistant alloy material according to claim 1, is characterized in that: rare earth elements RE is Rare Earth Elements Determination or mixed rare-earth elements.
3. Ag-W-RE high strength heat resistant alloy material according to claim 1 and 2, is characterized in that: rare earth elements RE comprises La, Ce, Pr, Nd, Er and Y.
4. Ag-W-RE high strength heat resistant alloy material according to claim 1, is characterized in that: hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that alloy constituent element is used.
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新型高强度铸造铝合金的研究;曾明等;《适用技术市场》;19971231(第5期);第3-4页 *
曾明等.新型高强度铸造铝合金的研究.《适用技术市场》.1997,(第5期),第3-4页.

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