CN102021378A - Cr-Li-RE high-strength heat-resistant aluminium alloy material and preparation method thereof - Google Patents
Cr-Li-RE high-strength heat-resistant aluminium alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN102021378A CN102021378A CN2009103067854A CN200910306785A CN102021378A CN 102021378 A CN102021378 A CN 102021378A CN 2009103067854 A CN2009103067854 A CN 2009103067854A CN 200910306785 A CN200910306785 A CN 200910306785A CN 102021378 A CN102021378 A CN 102021378A
- Authority
- CN
- China
- Prior art keywords
- alloy
- melt
- aluminium
- rare earth
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a high-strength heat-resistant aluminium alloy material and preparation method thereof. The aluminium alloy comprises the following components 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 Cr, 0.1-3.0% of Li, 0.05-5% of RE, and the balance of Al. By adopting high-quality melt, solid solution and phase diagram principle as a guide and preferably choosing alloy main elements Cu, Mn and RE formula, the method reduces the temperature range of the quasi-solid phase of the alloy, solves the problems of strong crack forming tendency in casting and low product strength at higher temperatures; by preferably choosing low-cost multi-component micro-alloying element formula, the method creates basic material conditions for the cultivation and the grain refining of medium-high and strengthening phases of the solid solution so as to finally prepare the high-strength heat-resistant aluminum alloy material.
Description
Technical field
The present invention relates to a kind of aluminum alloy materials and preparation method thereof, aluminum alloy materials of particularly a kind of micro alloying element and rare earth element and preparation method thereof.
Background technology
Aluminium alloy is a kind of younger metallic substance, just begins industrial application in 20 beginnings of the century.During the World War II, aluminium is mainly used in the manufacturing military aircraft.After the war, because war industry is die-offed to the demand of aluminium, the aluminium industry member is just started to develop civil aluminum alloy, make its range of application expand to construction industry, container package industry, transportation, electric power and national economy all departments such as electronic industry, machinery manufacturing industry and petrochemical complex, be applied in the middle of the daily life by aircraft industry.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 goods available temperature condition, aldural is divided into common aluminum alloy and high temperature (or heat-resisting) aluminium alloy again.Up to the present, can satisfy the high strength at high temperature needs, have only the Al-Cu line aluminium alloy, on trade mark series, Al-Cu is that alloy comprises cast aluminium alloy and wrought aluminium alloy, no matter and casting still is out of shape, all belong to 2 line aluminium alloys; And can satisfy the high-temp and high-strength aluminium alloy that good casting property is carried out deformation processing easily simultaneously, also do not see open the report.
1, high strength cast aluminum alloys and wrought aluminium alloy
General cast aluminium alloy comprises that AlSi system, AlCu system, AlMg system and AlZn are 4 series, wherein the intensity with AlCu system and AlZn line aluminium alloy is the highest, but it is most between 200Mpa～300Mpa, a few trade mark that has only AlCu system that is higher than 400Mpa, but because of 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 of obdurability is inferior slightly and is made its range of application be subjected to bigger restriction.Many important use such as extraordinary traction engine bogie wheel, aviation alloyed aluminium etc. adopts wrought aluminium alloy, rather than cast aluminium alloy.Wrought aluminium alloy has reduced defective by means such as extruding, rolling, forgings, refinement crystal grain, improved density, thereby had very high intensity, good toughness and good use properties.But, equipment and moulds of industrial equipment are required height, operation is many, so the wrought aluminium alloy production cycle is long, cost is very high.Compare plurality of advantages such as that cast aluminium alloy has is cheap, organize isotropy, can obtain special organization, be easy to produce complex-shaped part, can small serial production also can produce in enormous quantities with wrought aluminium alloy.Therefore, develop the high-toughness casting aluminum alloy material and the casting forming process thereof that can substitute the part wrought aluminium alloy, can reach the purpose of casting and forging, shortening manufacturing cycle, reduction manufacturing cost, have important significance for theories and great actual application value.
In the evolution of high-toughness casting aluminum alloy, the A-U5GT that 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.
On the A-U5GT basis, transform behind the U.S. aluminium association trade mark 201.0 (1986) and 206.0 (1967) and form, have good mechanical property and stress corrosion resistant ability.But owing to contain 0.4%～1.0% silver, material cost is very high, only is used for military affairs or other demanding fields, has limited its range of application.
In the high-toughness casting aluminum alloy field, China has obtained the achievement of attracting attention in the world.The sixties, the Beijing Research Inst. of Aeronautic Material succeeded in developing the ZL205A alloy to the seventies.ZL205A alloying constituent complexity contains Cu, Mn, Zr, V, Cd, Ti, 7 kinds of alloying elements such as B.The tensile strength of ZL205A (T6) is 510MPa, is that the cast aluminium alloy material intensity of the existing at present 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 a castability is poor, hot cracking tendency is big, and simultaneously because of the formulation cost height, range of application is little.
Above-mentioned 3 kinds of high-toughness casting aluminum alloys belong to Al-Cu system.This series alloy intensity height, plasticity and toughness are also better.But castability is relatively poor, is embodied in that hot cracking tendency is big, flowability is relatively poor, feeding is difficult.In addition, this series alloy etch resistant properties is relatively poor, and the intergranular corrosion tendency is arranged.The qualified casting of this series alloy is very low.
In addition, disclosed application number is that 4 patent names of 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 are in the document of " a kind of high-strength cast aluminium alloy material " and have introduced a kind of high-strength cast aluminium alloy material of being made up of Cu, Mn, Ti, Cr, Cd, Zr, B and rare earth element, this aluminum alloy materials has advantages of higher tensile strength and unit elongation, tensile strength has reached 440Mpa, and unit elongation is greater than 6%; But this type of high-strength cast aluminium alloy material in use still fails to solve the particularly thorny of the big problem of hot cracking tendency, alloy strength and castability, its major cause is at alloy principal element Cu, Mn composition range, the accurate solid-state temperature a wider range of alloy, provide sufficient condition for having anisotropic dendrite growth during casting solidification, form powerful internal contraction stress solidifying the later stage, so it is big to shrink hot cracking tendency.
The 2XXX of official registration is that the wrought aluminium alloy trade mark has more than 70 at present, the overwhelming majority is a U.S. Register, wherein have only 2001,2004,2011,14 trades mark such as 2011A, 2111,2219,2319,2419,2519,2021,2A16,2A17,2A20,2B16 be copper content at the high X alloy more than 5%, and wherein copper content is having only 2A16,2A17, these 4 trades mark of 2A20,2B16 more than 6%.All contain compositions such as more Si, Mg, Zn in these wrought aluminium alloy prescriptions, and there is not rare earth (RE) etc. to play the element of microalloying effect, therefore its prescription composition is that cast aluminium alloy differs greatly with 2, reflects the different production technique and the deep processing technology of aluminium alloy of two kinds of attributes.
2, high temperature aluminium alloys
Superalloy claims heat-resistance high-strength alloy, the strong alloy of heat or superalloy again, it is a kind of important meals material that grows up along with the appearance of aero-turbine in the forties in 20th century, can under high temperature oxidation atmosphere and exhaust gas corrosion condition, bear bigger working load for a long time, being mainly used in the hot-end component of internal combustion turbine, is the important structure material of aerospace, naval vessel, generating, petrochemical complex and communications and transportation industry.Wherein some alloy also can be used for biotechnology and makes orthopaedics and dental material.
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 bigger working load in the thermal environment midium or long term below 400 ℃, is more and more used in fields such as aerospace, heavy industry machineries.Except that aero-turbine, internal combustion turbine etc. directly with parts that high-temperature fuel gas contacts, all the other High Temperature High Pressure strong power parts all can adopt the heat-resistance high-strength aluminium alloy casting.
Because the aluminium alloy ratio is easier to processing, along with the raising of processing technology level, under the situation that intensity meets the demands, people adopt wrought aluminium alloy to substitute cast aluminium alloy more and more.Therefore the heat-resistance high-strength aluminium alloy is divided into Ajax alloy and distortion alloy two big classes again.
In general, the heat-resistance high-strength alloy all contains multiple alloy element, many reach ten surplus kind.The element that is added plays effects such as solution strengthening, dispersion-strengthened, grain-boundary strengthening and surface stabilization respectively in alloy, make alloy can at high temperature keep high mechanical property and environmental performance.
The factor that should consider when selecting casting for use 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 for the aluminum alloy materials of high temperature component casting at present, have only A201.0, ZL206, ZL207, ZL208,206.0 several trades mark in the national standard, comprise aluminum bronze Mn series alloy and aluminium rare earth-based alloy; Wherein, aluminum bronze Mn series alloy majority is an alloy material with high-purity grade of aluminium ingot, and cost is higher, and then at room temperature mechanical property is relatively poor relatively for the aluminium rare earth-based alloy.And, at present heat-resistance high-strength aluminium alloy ubiquity hot strength low (instantaneous tensile strength is less than 200Mpa more than 250 ℃, creep rupture strength is less than 100Mpa), formulation cost height, defectives such as castability is poor, casting qualified rate is low, waste product material and slag charge reuse difference, problem such as cause that casting quality is poor, cost height, slag charge treatment scheme are long.In addition, also all contain noble element in the new prescription of most heat-resisting aluminium alloy patents of declaring in recent years, and castability is poor, quality can't satisfy the requirement of aeronautical technology progressive, is unsuitable for the industrialization production application.
And the heat-resistance high-strength wrought aluminium alloy that in national economy and the modernization of national defense and development, has extensive use and the bright prospect of aurora, report is less in the domestic and foreign literature, known 2219,2A02,2A04,2A06,2A10,2A11,2A12,2A14,2A16,2A17,2A50,2A70,2XXX such as 2A80 are that 7XXX such as wrought aluminium alloy and 7A04 are wrought aluminium alloy, the intensity majority is less than 100Mpa under temperature more than 250 ℃, and its main alloy element is removed 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-resistance high-strength degree field of aluminum alloys both at home and abroad at present has as can be known: hot strength and weather resistance deficiency, and the high temperature instantaneous strength is all less than 250Mpa more than 250 ℃, and creep rupture strength is all less than 100Mpa; The materials processing poor performance; Waste disposal long flow path, cost height can't satisfy aeronautical technology progressive requirement etc.
Summary of the invention
Technical problem to be solved by this invention is, the melt treatment that exists at present aldural field is extensive, of poor quality, hot cracking tendency big, castability is poor, technical barriers such as the goods yield rate is low, hot strength is low, waste product material and slag charge reuse difference, with high-quality melt, sosoloid and phase diagram theory is guidance, by preferred alloy principal element Cu, Mn and rare earth element prescription, reduce the accurate solid-state temperature scope of alloy, the problem that is ubiquitous of big, the goods hot strength low (comprising instantaneous strength and creep rupture strength) of hot cracking tendency when solving casting; Preferred low-cost multicomponent microalloying element formula is for material base condition is created in the cultivation and the grain refining effect of high temperature phase and strengthening phase in the sosoloid; And optimize melting, thermal treatment process technology, realize high temperature phase and the enough culture of strengthening phase and giving full play to of grain refining effect in the sosoloid.The AlCu that finally develops a kind of rare earth multicomponent micro-alloying is novel high-strength heat-resisting (castibility and deformability) aluminum alloy materials.
Technical scheme of the present invention is, by weight percentage, this alloying constituent is Cu:1.0～10.0%, Mn:0.05～1.5%, Cd:0.01～0.5%, Ti:0.01～0.5%, B:0.01～0.2%, Zr:0.01～1.0%, Cr:0.01～1.0%, Li:0.1～3.0%, rare earth elements RE: 0.05～5%, all the other are Al.
Above-mentioned rare earth elements RE is single rare earth element 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, again as required the preparation the alloy total amount, extrapolate the quality of every kind of required elemental metals, the perhaps quality of master alloy, perhaps the quality of hybrid metal additive (comprising salt compounds) is worked out the alloy production allocation sheet, and gets the raw materials ready by allocation sheet choosing foot.
(2) add an amount of aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Mn, Ti, Zr, Cr, Li pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Cr, Al-Li master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive (comprising salt compounds) after stirring again, add B and rare earth elements RE again, stir.
Wherein, the hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used.Sintered metal product comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix; Flux is meant 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 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7), determine foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment in order to prevent the material burning.
Compared with prior art, the present invention has following major advantage:
To adopt refined aluminium mostly be matrix material and add the above noble element of thousandth to have solved present Al-Cu and be high tough aluminium alloy (ZL201A, ZL 204A, ZL 205A etc.), cost is higher, causing Al-Cu is that high tough aluminium alloy can only be used for leading-edge fields such as aerospace, defence and military, and civil area is used limited problem because of cost performance is not high.
Along with the continuous expansion in China of China and the quick growth of world aluminum output and aluminium industry size, " with aluminium for steel " day by day becomes the trend and the trend of industry development, and also presses for the high high tough aluminium alloy of cost performance at civil area; The present invention is a matrix material by adopting general aluminium, do not add (or adding less) noble element, preferred feature micro alloying element prescription, and adopt technologies such as intensive, terse founding, purification, develop the novel high-strength heat-resistant aluminium alloy material, overcome the threshold on cost of current material.
Particularly, the present invention has following eight advantages.
1, high strength and high rigidity.From the strength of materials, require under the prerequisite satisfying plasticity, can be by Technology means such as thermal treatments, make various strengthening phases in as-cast structure fully, evenly, rationally separate out and distribute, make the strength of materials reach 480～540MPa; Hardness 〉=HB140.
2, the double attribute of material.From the material applications attribute, it belongs to the both sexes aluminium alloy, the characteristic of existing cast aluminium alloy has the characteristic of wrought aluminium alloy again, both can be directly used in casting all kinds of light powerful spares and structural part, also can cast bar earlier and be hot extruded into section bar into various sections again.
In essence, this material belongs to the cast aluminium alloy of multicomponent microalloying, but because material has excellent flowing and intergranular self-lubricating property, makes it possess the easy processing characteristics of wrought aluminium alloy simultaneously.
3, the advance of technology.On production technique, on smelting technique, changed traditional extensive technology, can use electric furnace to carry out tight protectiveness melting, thereby avoid melt to sneak into too much impurity and gas, complicated follow-up melt treatment flow process has also been simplified and shortened to the purity that had both kept alloy; Simultaneously, fusion process has improved energy utilization rate greatly than the conventional reflective melting technology and has reduced pollution to environment, belongs to environment protecting and power-saving type technology.
(1) the protectiveness melting has significantly reduced energy consumption, pollution, has simplified Production Flow Chart, has improved the intensification degree
Because aluminium and aluminium alloy melt have extremely strong air-breathing tendency, so in the bad stove of open type or closure when thawing and melting, fused alloy liquid can absorb airborne O in large quantities
2, gas such as moisture, generate insoluble Al
2O
3With H with excellent activity
2, in melt, form impurity and gas, if untimely removing can form the slag inclusion, pore of foundry goods, defective such as loose when casting, cause goods to be scrapped; Wherein especially with H in the melt
2The harm maximum because H
2Solubleness when aluminium and aluminium alloy molten state is much higher than the solubleness when solid-state, therefore when solidifying, has a large amount of H
2From alloy, overflow and cause a large amount of defectives.Insoluble slag is then relatively more easily removed.Therefore, avoiding melt air-breathing is the important measures that keep melt quality and castability.
Common large scale industry aluminium alloy smelting stove is to be the reflector oven or the holding furnace of the energy with liquid or geseous fuel, needs a large amount of air-breathings, contains a large amount of water vapors and CO in the products of combustion simultaneously
2, NO
XDeng material, at high temperature very easily generate various detrimental impurity, simultaneously the same H that very easily adsorbs of these impurity itself with aluminium liquid with aluminium generation chemical reaction
2, make melt be subjected to severe contamination, before casting, melt must experience together or the special cleaning section in a few road, and the casting flow process of being allowed for access after the sampling detection is qualified, and this has prolonged work flow undoubtedly, and energy consumption and contamination index all are difficult to reduce; Because the continuity requirement of producing must make equipment maximize, increase investment simultaneously, improved the technology access threshold; To form multiplication long and the overhaul cost of equipment, start-up cost are all along with the maximization of equipment and long flow process.
And general aluminium alloy casting spare production plant, because production scale is little, equipment is simply extensive, and aluminium alloy melt is seldom taked airtight sfgd., causes melt quality and castability not high equally.
The preparation method that the present invention requires, its melting mode is to adopt the Induction Heating Equipment of with closure, air, water vapor and various products of combustion are to the pollution of melt when having eradicated fuel combustion, simultaneously in fusion process, can adopt protective gas to carry out the protective atmosphere melting, farthest the invasion and attack of secluding air; Owing to kept the high purity of melt, can take very simple through type degasification, deslagging device in cast sections thereafter, and needn't add special stop formula soaking equipment, thereby simplify technical process greatly.
(2) optimize the thermal treatment process of foundry goods, avoided the generation that material mechanical performance reduces, goods are scrapped that causes because of " burning "
Application number is 200810302670.3; 200810302668.6; 200810302669.0 and 4 patent names of 200810302671.8 are in the invention of " a kind of high-strength cast aluminium alloy material "; the heat treatment process parameter of prescribed material is " below 620 ℃; in 72 hours "; in the material application test; when temperature surpasses 560 ℃ when finding solution treatment; " burning " phenomenon usually can take place; cause the destruction of material microstructure; its characteristic feature is that leading indicators such as intensity and ductility significantly reduce; foundry goods becomes fragile; the surface blackening obfuscation, even in heat treatment process, promptly crack; the distortion and scrap.And when solid solubility temperature was lower than 470 ℃, because cultivation, the precipitation strength effect of strengthening phase are insufficient, the intensity of material was difficult to reach the desired destination value; Simultaneously,, find that heat treatment time surpasses 30 hours, the raising of material property is not had unusual effect through after test of many times gropes.Therefore, in order to improve effect and efficient, with heat treatment process parameter optimize and revise into: 470～560 ℃, 30 hours with interior solution treatment.
4, Pei Fang science and economy.From raw material sources, advanced prescription has been created the advantage body material advantage and the alloying element advantage of two aspects.On the one hand, the matrix alloy of novel material series can adopt general industry fine aluminium (promptly two zero aluminium, comprise aluminium liquid and remelting aluminium ingot), must adopt refined aluminium or the high-purity grade of prescription model that aluminium is matrix alloy than existing aldural, have advantages such as raw material supply abundance, cost is low, buying is convenient; Simultaneously, this material can adopt refined aluminium or high-purity grade of aluminium as matrix alloy equally, and the material of this prescription has higher ductility than the general alumina-base material of this kind.On the other hand, the contribution rate that cost of alloy is raise because of noble element is the tens of of common element and even more than hundred times, majority does not adopt noble element in the combination of the alloying element of novel material series, even adopt, ratio is also very little, all below thousandth; And the ratio of existing aldural noble element is all more than thousandth, and the advantage of two aspects is that serial novel material opens up a market and laid in great potential.
The present invention is the polynary prescription of feature micro alloying element by preferred alloy principal element copper (Cu), manganese (Mn) with chromium (Cr), lithium (Li), for material base condition is created in the cultivation and the grain refining effect of high temperature phase and strengthening phase in the sosoloid, alloy forms at principal element Cu, Mn and strengthens θ phase (Al
2Cu), T phase (Al
12Mn
2Cu) on the basis, select high temperature elemental chromium (Cr), lithium (Li) and the rare earth elements RE trace additives as complex alloysization for use, Cr forms β-CrAl in alloy
7, η-Cr
25 kinds of dispersivity High-Temperature Strengthening such as Al phase, Li forms Al in alloy
2Li
3, AlLi
5Deng 5 kinds of dispersivity High-Temperature Strengthening phases, can improve hardness of alloy and corrosion resisting property; Rare earth elements RE can form multiple metallic compound in aluminium alloy (have α-Al as the aluminium lanthanum
11La
3, β-Al
11La
3, AlLa
3Deng, the aluminium cerium has α-Ce
3Al
11, CeAl
3, CeAl
2Deng, the aluminium praseodymium has α-Al
11Pr
3, ρ-AlPr
3Deng, the aluminium neodymium has α-Al
11Nd
3, AlNd
3Deng, the aluminium promethium has Al
11Pm
3, AlPm
2Deng, the aluminium samarium has Al
11Sm
3, AlSm
2Deng, the aluminium europium has Al
4Eu, AlEu etc., the aluminium gadolinium has Al
4Gd, Al
17Gd
2Deng, the aluminium terbium has Al
3Tb, AlTb
2Deng, the aluminium dysprosium has α-Al
3Dy, AlDy
2Deng, the aluminium holmium has Al
3Ho, AlHo
2Deng, the aluminium erbium has Al-Er:Al
3Er, AlEr
2Deng, the aluminium thulium has Al
3Tm, AlTm etc., the aluminium ytterbium has Al
3Yb, Al
2Yb etc., the aluminium lutetium has Al
3Lu, AlLu
2Deng, the aluminium yttrium has Al
3Y, AlY
2Deng, the aluminium scandium has Al
3Sc, AlSc
2Deng, total nearly hundred kinds of infusibility active metallic compounds), all significantly improved alloy at room temperature intensity, high-temperature capability and fluidity of molten.
The main alloying element mechanism of action of the present invention is as follows.
1. this material allows copper (Cu) content in 1～10% scope, is that cast aluminium alloy cupric (Cu) amount is that 3～11% scope is slightly different than Al-Cu, but in theory then has earthshaking innovative significance.
On the one hand, at copper (Cu) content is 5.65～5.7% o'clock, just in time equal the eutectic solubleness of Cu in the Al-Cu alloy, the turn model and the mechanism of action according to " fully solid solution-evenly separate out-grain-boundary strengthening phase-brilliant crack weighting agent (bond, inlay, anti-skidding) " in heat treatment process change, and form more rich Cu strengthening phase (comprising Al
2Cu is the 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, the strong on one side tendency that increases ground rich Cu strengthening phase of discharge outside crystal boundary, cause structural stress huge between intracrystalline and crystal boundary, alloy monolithic is in the solidification shrinkage stage simultaneously, string stress and structural stress are superimposed, when the instant actual strength that surpasses alloy, then form thermal crack, therefore in the certain limit of copper (Cu) content≤5.65%, the castability of aluminium alloy is the poorest, the hot cracking tendency maximum.But total trend is that along with the reduction of copper content, the hot cracking tendency of alloy also reduces; When Cu content＜1%, its strengthening phase deficiency, the turn model of strengthening phase and the mechanism of action are difficult to give full play to, separating out and can form more defective between crystal boundary when temperature variation at crystal boundary to dissolving in of intracrystalline, reduce alloy at room temperature and hot strength, so it is Cu content is low excessively, nonsensical concerning simple Al-Cu alloy; If but added more rare earth element (RE) in the alloy, then could play remedying the low excessively special-effect of Cu content.
On the other hand, at Cu content 〉=5.7% o'clock, rich Cu can not all be absorbed by matrix when thermal treatment, then be distributed in crystal boundary with border rich Cu metallic compound form disperse, reduced the concentration difference of the inside and outside Cu particle of α-Al sosoloid, mild α-Al sosoloid dendrite is discharged the intensity of rich Cu phase to crystal boundary in process of setting, has promptly reduced structural stress and hot cracking tendency.Obviously, when Cu content 〉=5.7%, rich Cu is many more mutually, and the structural stress of alloy inside and hot cracking tendency are more little during crystallization; Simultaneously, the rich Cu of the thin brilliant disperse of high-melting-point forms active heterogeneous nucleus when melt crystallization, quicken the melt crystallization reaction but stop nuclei growth, refinement crystal grain, also reduced the alloy hot cracking tendency; And make between the matrix crystal boundary filling fuller; Rich Cu can also form the refractory metal compound with multiple element such as Al, Mn mutually.All these effects, the surface tension of the melt that weakened has significantly reduced melt viscosity, thereby has significantly improved the castability of fluidity of molten and alloy.
When Cu content is in 5.7% left and right sides, after heat treatment, at the matrix crystal boundary more rich Cu phase (dissolving in-precipitated phase) and the less thin brilliant disperse phase of (about 0.5%) Cu based metallization compound are arranged, make the alloy strength under the room temperature state keep higher level, but when being in hot environment, because of a large amount of rich Cu dissolve in the matrix mutually again, will cause more intergranular space and defective, this can make the hot strength of alloy significantly descend.Along with Cu content continue to increase, the degree of alloy strength temperature influence reduces, and when disperse phase and precipitated phase were in the equivalent state substantially, it is minimum that the strength of materials is acted upon by temperature changes, and Cu content should be 11～12% in the alloy at this moment.
But when Cu content in the alloy＞10%, the Cu of surplus has preferential crystallization character mutually and forms huge network structure during because of crystallization, alloy viscosity strengthens greatly, surplus replaces the principal element that aluminum substrate becomes crystallization control in crystallisation process, original disperse phase is all shielded the good effect of aluminum substrate phase, so the various performances of alloy decline to a great extent again.
According to the checking of above theoretical basis and practice, determine that the zone of reasonableness of main alloying element Cu content is: 1～10% (wt%)
2. this material improves corrosion stability with manganese (Mn) element, shields impurity F e simultaneously, reduces the deleterious effect of Fe.
Because of manganese (Mn) element has identical current potential with MnAl6 and the fine aluminium that the matrix effect generates, can improve the corrosion stability and the weldability of alloy effectively; While, Mn was as the High-Temperature Strengthening phase, had the effect that improves recrystallization temperature, suppresses the recrystal grain alligatoring, can realize the solution strengthening to alloy, additional reinforcement, raising resistance toheat; Under the grain-refining agent effect, can generate the Al of pelletizing shape with the Fe element
3(Fe, Mn) effectively eliminated the deleterious effect of Fe to alloy, so the present invention can allow the scope (Fe≤0.5%) of Fe content at broad, and the benefit of bringing like this is: realize general aluminium substitution refined aluminium, reduce cost, enlarge raw material sources and material Application Areas.
3. mainly use rare earth RE as basic micro alloying element, and its content range is big, reach as high as 5%, can give full play to degasification, slagging-off, cleaning action, crystal grain thinning and the metamorphism of rare earth element in alloy, the mechanical property and the solidity to corrosion effect of raising alloy.
The mechanism of rare earth element degasification, slagging-off, cleaning action is: rare earth element is very strong in activity, and oxygen, hydrogen, sulphur, nitrogen etc. are had stronger avidity, and its deoxidizing capacity surpasses the strongest existing 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 compound such as Al between stable refractory metal in aluminium alloy
4RE, Al
8CuRE, Al
8Mn
4RE, Al
24RE
3Mn etc.Between these refractory metals the compound disperse is 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,, therefore thermotolerance and the wear resistance that improves alloy all had good effect because its fusing point and hardness are very high.In addition, also can in and low melting point impurity element Sn, Pb, Sb etc. in the molten metal, form dystectic compound with them or make they from the interdendritic in whole crystal uniform distribution, eliminated dendritic structure.
Rare earth element has crystal grain thinning and metamorphism.Rare earth element is a surface active element, can concentrate to be distributed on the crystal boundary face, reduces melt viscosity, strengthens flowability, reduces pulling force between phase and phase, because the merit that forms the critical size nucleus is reduced, nuclei of crystallization quantity increases, thereby makes grain refining.Rare earth has long-lasting and remelting stability to the metamorphism of aluminium alloy, and most ofs single or mishmetals add then has very strong refinement and metamorphism mutually to α-Al.
In addition, rare earth element can also improve the electroconductibility of alloy.Because rare earth energy refinement aluminium grain also can form stable compound (as CeFe by impurity such as Fe, Si in alloy
5, CeSi, CeSi
2Deng) and separate out from intracrystalline, add the cleaning action of rare earth to alloy, make the resistivity of aluminium be reduced, electroconductibility improves (about 2%).
Very a spot of rare earth elements RE can produce significantly rotten improving effect to alloy property, therefore, the rare earth adding quantity of general aluminium alloy is below 1%, in 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 patent applications, content of rare earth is defined as 0.05～0.3%.Analyze from the Al-RE alloy phase diagram, because the solubleness of most of rare earth in aluminium very little (being about 0.01% as Ce), it exists, and form is many to be distributed in crystal boundary or basic intracrystalline portion with compound between refractory metal.Because activity is very high, in cleaning molten, serve as scavenging agent and consume a part, if add-on is very little, then its metamorphism to α-Al phase just is difficult to give full play to.Be the metamorphic long-lasting and remelting stability of maintenance rare earth, and give full play to its High-Temperature Strengthening characteristic, the present invention is special to be considered copper content with content of rare earth, determine that its content range is 0.05～5%.
4. chromium (Cr) element adds element as the feature of complex alloysization, can form β-CrAl in alloy
7, η-Cr
25 kinds of dispersivity High-Temperature Strengthening such as Al phase, lithium (Li) element adds element as the feature of complex alloysization, can form Li and form Al in alloy in alloy
2Li
3, AlLi
5Deng 5 kinds of dispersivity High-Temperature Strengthening phases, can improve hardness of alloy and corrosion resisting property.
5, You Yi castability.By the foundry goods that uses at several fields such as high-tech structure, Aeronautics and Astronautics, civilian heavy industrys foundry trial repeatedly, verified the excellent properties of this novel material: castability is higher than present A201.0, ZL206, ZL207, ZL208, high strength cast aluminium alloys such as 206.0, the significant problem that hot cracking tendency is big, casting qualified rate is low when having solved above-mentioned aluminium alloy casting; Old material melts down remelting and virgin material can be realized the arbitrary proportion batching, new and old material blend melt casting performance does not have change, and the good action that stable material intensity, raising ductility are arranged, the situation that the reuse of more original aldural waste material is poor, circulation route is long has utmost point remarkable economical and intensivism.
The principle that novel material is eliminated hot cracking tendency is: form rich Cu phase because of copper content in the alloy increases, rich Cu is distributed in crystal boundary as the thin brilliant disperse phase of high-melting-point with the disperse of metallic compound form, the strong tendency that spreads to crystal boundary of having offset effectively when melt crystallization that the rich Cu solute of intragranular forms because of degree of supersaturation sharply raises, thereby the structural stress when having slowed down crystallization; The multiple disperse phase of rich Cu disperse phase and Cr, Li feature micro alloying element, RE microalloying of rare earth element and Mn, Zr, 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, guaranteed that cast article has 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 the atom bloc framework and the fine crystalline structure of an alloy melt formation, a large amount of active nucleus can be given full play to the effect of cohesion, assimilation microlitic structure in melt, and can keep original flowability.Therefore, the good action of allocating stable material intensity, raising ductility into of old material.
This specific character of old material can be implemented in the instant reuse of production scene fully, no matter is slag charge, processing clout or rejected casting, all can with together melting or directly add in the melt of virgin material.
This specific character of the present invention, 1XXX system and the 2XXX series high strength aluminum alloy materials qualified casting widely applied at present significantly improve, greatly reduce rejection number, therefore do not need big waste product stockyard (in the actual production, very big scrapground ground often will be cooked up in the aluminium alloy casting workshop) in the production scene; Simultaneously, a lot of cast aluminium alloys do not possess remelting stability, and therefore direct reuse needs group to criticize and focus at the scene, occupies very big manufacturing cost, derives a series of processing links and fruitless labour; And use novel material provided by the invention, all these extra links, cost and fruitless labour all can be saved.
6, You Yi processing, surface anticorrosion handling property.By novel material being processed into the test of the finished parts of different shapes such as axle, ball, pipe, angle section, bolt, testimonial material has fabulous processability, and the surface can reach the fine and clean degree of nearly minute surface degree, and luminous reflectance factor is higher than fine aluminium; Surface oxidation and coated test show that thickness can reach the standard-required grade after the surperficial anodic oxidation, surface color does not have change, and the tack of coating and oxidized surface reaches the standard class of resistance to rupture test fully.
7, You Yi high-temperature behavior.This material has the characteristic of high temperature aluminium alloys, can reach that intensity is higher than more than the 200Mpa under 400 ℃ of conditions, be higher than traditional high temperature (heat-resisting) aluminum alloy materials, this characteristic makes novel material can substitute other each position heat-resistant part material except that 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 Cr, Li etc.).
8, typical original.This series type material is that the applicant develops after obtaining alloying theory innovation breakthrough fast, the checking of material excellent properties is exactly the checking to the new alloy theory simultaneously, therefore and this theoretical breakthrough was not all clearly put down in writing on all documents and materials at present, should the series novel material belongs to primitiveness, basic great innovation in the world.
Innovative point of the present invention
Table one listed with the present invention in one aspect performance and purposes on close 31 kinds of aluminium alloys elementary composition.As can be seen, compare with existing various high copper content wrought aluminium alloies, heat-resistant deforming aluminium alloy, birmastic, the present invention mainly contains following innovative content.
The one, copper (Cu) content allowed band is big, 1～10%; Cooperate with manganese (Mn) element simultaneously and form multiple High-Temperature Strengthening phase.
The 2nd, mainly use rare earth RE as basic micro alloying element, and its content range is big, reach as high as 5%, can give full play to degasification, slagging-off, cleaning action, crystal grain thinning and the metamorphism of rare earth RE in alloy, the mechanical property and the solidity to corrosion effect of raising alloy; Rare earth elements RE is all very strong to the avidity of oxygen, sulphur, nitrogen, hydrogen, thereby the effect of its deoxidation, desulfurization, removal hydrogen and nitrogen is all very strong, in addition, RE is a 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 has opened up the space for using general aluminium to carry out the founding of alloy material as matrix.
The 4th, do not use low melting point elements such as magnesium, zinc as the material that produces strengthening phase, avoid the 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 chromium (Cr) element as the feature of complex alloysization, in alloy, can form β-CrAl
7, η-Cr
25 kinds of dispersivity High-Temperature Strengthening such as Al phase, lithium (Li) element adds element as the feature of complex alloysization, can form Al in melt
2Li
3, AlLi
5Deng 5 kinds of dispersivity High-Temperature Strengthening phases, can improve hardness of alloy and corrosion resisting property; Be used in combination 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 tangible five aspects in the characteristic formula of the present invention.
The various aluminum alloy chemically compositions that table one is relevant with the present invention
Mechanical property relatively
The applicant compares the present invention with the mechanical property of existing several high tough aluminium alloys, see Table two.
The mechanical property of table two the present invention and several high-toughness casting aluminum alloys
1. institute's column data is 206.0 high-purity alloys, i.e. W (Si)≤0.05%, W (Fe)≤0.10%.S-sand mold casting, J-permanent mold casting, R-investment cast
As can be seen from Table II, tensile strength 480～540MPa of the present invention, hardness obviously is better than the mechanical property of existing high tough aluminium alloy greater than HB140.
3, high-temperature behavior
The applicant tests the intensity high temperature endurance performance of the present invention under all temps condition, and contrasts with the existing high temperature endurance performance of using heat-resisting aluminium alloy always, sees Table three.
The high temperature endurance performance of table three the present invention and heat-resisting aluminium alloy commonly used
As can be seen from Table III, room temperature strength of the present invention is greater than 450Mpa, and more than 300Mpa, during 300 ℃ of hot strengths, high temperature endurance performance obviously is better than the high-temperature and durable of existing heat-resistance high-strength alloy greater than 200Mpa during 250 ℃ of hot strengths.
In sum, Cr-Li-RE high strength heat resistant alloy material of the present invention has the Application Areas of high-tech content, the length and breadth of land and splendid market outlook, its extremely excellent cost performance makes it can substitute present nearly all aldural and high temperature aluminium alloys, has represented the developing direction of the light strong structured material in the China and even the world.
Embodiment
Embodiment 1:Cu-1.0%, feature micro alloying element-Cr, Li, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare-earth elements La again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 485Mpa, unit elongation 7.5%.
Embodiment 2:Cu-4.2%, feature micro alloying element-Cr, Li, basic microalloying rare-earth elements La, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare-earth elements La, Ce mishmetal again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 538Mpa, unit elongation 7.4%.
Embodiment 3:Cu-5.1%, feature micro alloying element-Cr, Li, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare earth element Eu again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 503Mpa, unit elongation 6.1%.
Embodiment 4:Cu-6.01%, feature micro alloying element-Cr, Li, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare-earth elements La, Ce, Pr mishmetal again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 533Mpa, unit elongation 7.1%
Embodiment 5:Cu-6.5%, feature micro alloying element-Cr, Li, basic microalloying rare earth element er Er (1) is by the good required various alloying elements of charge calculation table weighing, and is as follows.
(2) add an amount of aluminium ingot in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare earth element er again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 527Mpa, unit elongation 6.9%.
Embodiment 6:Cu-7%, feature micro alloying element-Cr, Li, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare earth element nd again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 517Mpa, unit elongation 5.2%.
Embodiment 7:Cu-8%, feature micro alloying element-Cr, Li, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare earth element ce again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 501Mpa, unit elongation 4.8%.
Embodiment 8:Cu-10%, feature micro alloying element-Cr, Li, 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 is incubated down at 700～800 ℃; For preventing that melt from sucking too much air, melting process should be finished as far as possible at short notice with in the enclosed environment.
(3) add Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) earlier by formula rate again, add Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare earth element y again, stir.
The hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.Flux is meant 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 be operated in enclosed environment as far as possible simultaneously.
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 487Mpa, unit elongation 4.3%.
Claims (8)
1. Cr-Li-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%, Cr:0.01～1.0%, Li:0.1～3.0%, rare earth elements RE: 0.05～5%, all the other are Al.
2. Cr-Li-RE high strength heat resistant alloy material according to claim 1 is characterized in that: rare earth elements RE is single rare earth element or more than one mixed rare-earth elements.
3. Cr-Li-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. a Cr-Li-RE high strength heat resistant alloy preparation methods as claimed in claim 3 is characterized in that: comprise the steps:
(1) in above-mentioned element ratio scope, a selected group element ratio, again as required the preparation the alloy total amount, extrapolate the quality of every kind of required elemental metals, the perhaps quality of master alloy, perhaps the quality of hybrid metal additive is worked out the alloy production allocation sheet, and gets the raw materials ready by allocation sheet choosing foot;
(2) add an amount of aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and is incubated down at 700～800 ℃; Melting process is finished in enclosed environment;
(3) press formula rate again and add Mn, Ti, Zr, Cr, Li pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Cr, Al-Li master alloy or hybrid metal additive earlier, add Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive after stirring again, add B and rare earth elements RE again, stir;
(4) then above-mentioned alloy melt is carried out furnace refining; Add refining agent in alloy melt, and stir, the melt refining is operated in enclosed environment;
(5) slag hitting after the refining, leave standstill, temperature adjustment to 630～850 ℃, alloy liquid is toppled over and is come out of the stove, online degasification, slagging-off are handled;
(6) casting;
(7) foundry goods is carried out 470～560 ℃, 30 hours with interior solution treatment.
5. Cr-Li-RE high strength heat resistant alloy preparation methods according to claim 4 is characterized in that: the hybrid metal additive is meant interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used.
6. Cr-Li-RE high strength heat resistant alloy preparation methods according to claim 5 is characterized in that: sintered metal product comprises that manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mix.
7. Cr-Li-RE high strength heat resistant alloy preparation methods according to claim 6 is characterized in that: flux is meant the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na3AlF6.
8. Cr-Li-RE high strength heat resistant alloy preparation methods according to claim 4 is characterized in that: in step (4), refining agent is meant chlorine, hexachloroethane, Manganous chloride tetrahydrate and boron salt alterant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910306785.4A CN102021378B (en) | 2009-09-09 | 2009-09-09 | Cr-Li-RE High-strength heat-resistant aluminum alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910306785.4A CN102021378B (en) | 2009-09-09 | 2009-09-09 | Cr-Li-RE High-strength heat-resistant aluminum alloy material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102021378A true CN102021378A (en) | 2011-04-20 |
| CN102021378B CN102021378B (en) | 2015-12-09 |
Family
ID=43863153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910306785.4A Expired - Fee Related CN102021378B (en) | 2009-09-09 | 2009-09-09 | Cr-Li-RE High-strength heat-resistant aluminum alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102021378B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741103A (en) * | 2017-06-06 | 2020-01-31 | 伊苏瓦尔肯联铝业 | Lithium-containing aluminum alloys with improved fatigue properties |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180291489A1 (en) * | 2017-04-11 | 2018-10-11 | The Boeing Company | Aluminum alloy with additions of copper, lithium and at least one alkali or rare earth metal, and method of manufacturing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319287B (en) * | 2008-07-09 | 2011-03-16 | 贵州大学 | High-strength cast aluminium alloy material |
-
2009
- 2009-09-09 CN CN200910306785.4A patent/CN102021378B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110741103A (en) * | 2017-06-06 | 2020-01-31 | 伊苏瓦尔肯联铝业 | Lithium-containing aluminum alloys with improved fatigue properties |
| CN110741103B (en) * | 2017-06-06 | 2022-03-25 | 伊苏瓦尔肯联铝业 | Lithium-containing aluminum alloys with improved fatigue properties |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102021378B (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101805858B (en) | Li-RE high-strength heat-resistance aluminum alloy material and preparation method thereof | |
| CN101805844B (en) | Be-Cr-RE high-strength heat-resisting aluminum alloy material and production method thereof | |
| CN101805847B (en) | Co-Ni-RE high-strength heat-resisting aluminum alloy material and production method thereof | |
| CN101805855B (en) | Co-RE high-strength heat-resisting aluminum alloy material and production method thereof | |
| CN101805846B (en) | Mo-W-RE high-strength heat-resistance aluminium alloy material and preparation method thereof | |
| CN101805845B (en) | Li-Nb-RE high-strength heat-resistance aluminium alloy material and preparation method thereof | |
| CN101994034A (en) | Cr-Ni-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN101994038A (en) | Li-Ni-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN101994036A (en) | Mo-Ni-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN101994032B (en) | Be-Nb-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN102021371B (en) | Co-Cr-RE aluminium alloy material with high strength and heat resistance and preparation method thereof | |
| CN102021370A (en) | Be-Ni-RE high-strength heatproof aluminum alloy material and preparation method thereof | |
| CN102021366A (en) | Be-Co-RE high-strength heat-resistant aluminum alloy material and preparation method thereof | |
| CN102021373B (en) | Co-Li-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN102021374B (en) | Co-Nb-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN102021378A (en) | Cr-Li-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN101994042A (en) | Ni-W-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN102021376B (en) | Cr-Nb-RE high-strength heat-resistant aluminum alloy material and preparation method thereof | |
| CN102021369A (en) | Be-Li-RE high-strength heat-resistant aluminum alloy material and preparation method thereof | |
| CN101994035A (en) | Mo-Nb-RE high-strength heat-resistant aluminium alloy material and preparation method thereof | |
| CN102021441A (en) | Cr-RE high-strength heat-resistant aluminum alloy material and preparation method thereof | |
| CN102021367A (en) | Be-Mo-RE high strength heat resistant aluminium alloy material and preparation method thereof | |
| CN102021397A (en) | Ag-Li-RE high-strength heat-resistant aluminum alloy material and preparation method thereof | |
| CN102021372B (en) | Co-Mo-RE high-strength heat resistant aluminum alloy material and preparation method thereof | |
| CN102021377B (en) | Nb-W-RE high-strength heat-resistant aluminum alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151209 Termination date: 20170909 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |