CN102021378B - Cr-Li-RE High-strength heat-resistant aluminum alloy material and preparation method thereof - Google Patents
Cr-Li-RE High-strength heat-resistant aluminum alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of High-strength heat-resistant aluminum alloy material and preparation method thereof, its composition is Cu:1.0 ~ 10.0% by weight percentage, 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%, RE:0.05 ~ 5%, all the other are Al.The present invention for instructing, by preferred alloy principal element Cu, Mn and RE formula, reduces the accurate solidus temperature gap of alloy with high-quality melt, sosoloid and phase diagram theory, solves the problems such as hot cracking tendency when casting is large, goods hot strength is low; Preferred low cost multicomponent microalloying element formula, for material base condition is created in the cultivation of high-temperature-phase in sosoloid and strengthening phase and grain refining effect, finally develops a kind of 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, particularly the aluminum alloy materials and preparation method thereof of a kind of micro alloying element and rare earth element.
Background technology
Aluminium alloy is a kind of younger metallic substance, just starts industrial application in 20 beginnings of the century.World War II, aluminium is mainly for the manufacture of military aircraft.After the war, because the demand of war industry to aluminium die-offs, aluminum i ndustry circle just starts to develop civil aluminum alloy, make its range of application expand to each department of national economies such as construction industry, container package industry, transportation, electric power and electronic industry, machinery manufacturing industry and petrochemical complex by aircraft industry, 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 class; From goods can temperature condition divide, 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 system alloy comprises cast aluminium alloy and wrought aluminium alloy, no matter and casting or be out of shape, all belong to 2 line aluminium alloys; And the high-temp and high-strength aluminium alloy that good casting property easily carries out deformation processing can be met simultaneously, also do not see open report.
1, high strength cast aluminum alloys and wrought aluminium alloy
General cast aluminium alloy comprises AlSi system, AlCu system, AlMg system and AlZn system 4 series, wherein the highest with the intensity of AlCu system and AlZn line aluminium alloy, but majority is between 200Mpa ~ 300Mpa, higher than a few trade mark only having AlCu system of 400Mpa, but because adopting refined aluminium matrix and adding noble element, manufacturing cost is very high; The resistance toheat of AlZn system casting alloy is very poor.Therefore, general cast aluminium alloy makes its range of application be subject to larger restriction because obdurability is slightly inferior compared with wrought aluminium alloy.Many important use such as extraordinary traction engine bogie wheel, aviation alloyed aluminium etc. adopt wrought aluminium alloy more, instead of cast aluminium alloy.Wrought aluminium alloy decreases defect by means such as extruding, rolling, forgings, and refinement crystal grain, improves density, thus have very high intensity, excellent toughness and good use properties.But require high to process equipment mould, operation is many, therefore the wrought aluminium alloy production cycle is long, cost is very high.Compared with wrought aluminium alloy, cast aluminium alloy have cheap, organize isotropy, special tissue can be obtained, be easy to produce complex-shaped part, small serial production the plurality of advantages such as also can to produce in enormous quantities.Therefore, developing can the high-toughness casting aluminum alloy material of Substitute For Partial wrought aluminium alloy and casting forming process thereof, the object that can reach casting and forging, shorten the manufacturing cycle, reduce manufacturing cost, has important theory significance and great actual application value.
In the evolution of high-toughness casting aluminum alloy, the A-U5GT that succeeds in developing in 20 beginnings of the century of France occupies an important position, in high-toughness casting aluminum alloy representative at present its history at most, be most widely used.The trade mark that China is not corresponding with it at present.
Behind the US aluminum association trade mark 201.0 (1986) and 206.0 (1967), transformation and being formed on A-U5GT basis, has good mechanical property and stress corrosion resistant ability.But owing to containing the silver of 0.4% ~ 1.0%, material cost is very high, only requires high field for military affairs or other, limits its range of application.
In high-toughness casting aluminum alloy field, China achieves the achievement attracted 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, containing 7 kinds of alloying elements such as Cu, Mn, Zr, V, Cd, Ti, 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 the maximum defect of ZL205A is that castability is poor, hot cracking tendency large, and simultaneously because formulation cost is high, range of application is little.
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 to be inclined to.The qualified casting of this series alloy is very low.
In addition, disclosed application number be 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 4 patent names be in the document of " a kind of high-strength cast aluminium alloy material " and describe a kind of high-strength cast aluminium alloy material be made up 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 reaches 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 hot cracking tendency large problem, alloy strength and castability, its major cause is at alloy principal element Cu, Mn composition range, the accurate solidus temperature gap of alloy is wider, sufficient condition is provided for having the growth of anisotropic dendrite during casting solidification, phase forms powerful internal contraction stress after solidification, so it is large to shrink hot cracking tendency.
The 2XXX system wrought aluminium alloy trade mark of current official registration has more than 70, the overwhelming majority is U.S. Register, wherein only have 2001,2004,2011,2011A, 2111,2219,2319,2419,2519,2021,14 trades mark such as 2A16,2A17,2A20,2B16 are the high X alloy of copper content more than 5%, and wherein copper content only has these 4 trades mark of 2A16,2A17,2A20,2B16 more than 6%.The compositions such as more Si, Mg, Zn are all contained in these wrought aluminium alloies formula, 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 the production technique that the aluminium alloy of two attribute is different and deep processing technology.
2, high temperature aluminium alloys
Superalloy is also known as heat-resistance high-strength alloy, the strong alloy of heat or superalloy, it is a kind of important meals material grown up along with the appearance of aero-turbine in the forties in 20th century, larger working load can be born for a long time under high temperature oxidative atmosphere and exhaust gas corrosion condition, being mainly used in the hot-end component of internal combustion turbine, is the important feature 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 Ni-based, iron-based and cobalt base alloy, can work under 600 ~ 1100 DEG C of hot environments; Heat-resisting aluminium alloy grows up during being then cold war.Heat-resistance high-strength aluminium alloy is suitable for bearing larger working load for a long time in the thermal environment below 400 DEG C, is more and more applied in fields such as aerospace, heavy industry machineries.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 heat-resistance high-strength aluminium alloy to cast.
Because aluminium alloy ratio is easier to processing, along with the raising of processing technology level, when 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 distortion alloy two.
In general, heat-resistance high-strength alloy all contains multiple alloy element, and many reaches more than ten kinds.The element added plays the effects such as solution strengthening, dispersion-strengthened, grain-boundary strengthening and surface stabilization in the alloy respectively, makes alloy can at high temperature keep high mechanical property and environmental performance.
Select the factor should considered during casting superalloy:
(1) frequency of the normal working temperature of foundry goods, the highest and minimum working temperature and temperature variation.
(2) temperature range of foundry goods itself and the expansion character of alloy.
(3) load performance that bears of foundry goods, loads, 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.
At present for the aluminum alloy materials of high temperature component casting, only have A201.0, ZL206, ZL207, ZL208,206.0 several trades mark in national standard, comprise aluminum bronze Mn series alloy and aluminium rare earth-based alloy; Wherein, aluminum bronze Mn series alloy majority is with high-purity grade of aluminium ingot for alloy material, and cost is higher, and then at room temperature mechanical property is relatively poor for aluminium rare earth-based alloy.And, current heat-resistance high-strength aluminium alloy ubiquity hot strength, and low (more than 250 DEG C instantaneous tensile strength are less than 200Mpa, creep rupture strength is less than 100Mpa), the defect such as formulation cost is high, castability is poor, casting qualified rate is low, waste product material and slag charge reuse difference, the problem such as cause that casting quality is poor, cost is high, slag charge treatment scheme is grown.In addition, most heat-resisting aluminium alloy patents of declaring in recent years also all contain noble element in newly filling a prescription, and castability is poor, and quality cannot meet the requirement of aeronautical technology progress, is unsuitable for industrialization production application.
And there is the heat-resistance high-strength wrought aluminium alloy of extensive use and pole the bright outlook in national economy and the modernization of national defense and development, report less in domestic and foreign literature, known 2219, 2A02, 2A04, 2A06, 2A10, 2A11, 2A12, 2A14, 2A16, 2A17, 2A50, 2A70, the 7XXX system wrought aluminium alloies such as 2XXX system wrought aluminium alloy and 7A04 such as 2A80, more than 250 DEG C, at 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 element, and intensity is not reported at the heat-resistance high-strength wrought aluminium alloy material of more than 150Mpa at more than 250 DEG C temperature.
In sum, known at present domestic and international in the research of heat-resistant high-strength field of aluminum alloys Problems existing have: hot strength and weather resistance are not enough, and more than 250 DEG C 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 etc. of aeronautical technology progress.
Summary of the invention
Technical problem to be solved by this invention is, the melt treatment existed for current aldural field is extensive, of poor quality, hot cracking tendency is large, castability is poor, goods yield rate is low, hot strength is low, the technical barriers such as waste product material and slag charge reuse difference, with high-quality melt, sosoloid and phase diagram theory are for instructing, by preferred alloy principal element Cu, Mn and rare earth element formula, reduce the accurate solidus temperature gap of alloy, solve hot cracking tendency when casting large, the problem be ubiquitous of goods hot strength low (comprising instantaneous strength and creep rupture strength), preferred low cost multicomponent microalloying element formula, for material base condition is created in the cultivation of high-temperature-phase in sosoloid and strengthening phase and grain refining effect, and optimize melting, thermal treatment process technology, realize the enough culture of high-temperature-phase and strengthening phase in sosoloid and giving full play to of grain refining effect.Finally develop a kind of AlCu system novel high-strength heat-resisting (castibility and deformability) aluminum alloy materials of rare earth multicomponent micro-alloying.
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 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 prepared as required again, extrapolate the quality of often 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 is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) 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) is first added by formula rate again, Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive (comprising salt compounds) is added again after stirring, add B and rare earth elements RE again, stir.
Wherein, hybrid metal additive refers to interpolation, the pie adjusting alloy constituent element or block non-sintered sintered metal product.Sintered metal product comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes; Flux refers to that the mixture of basic metal or alkaline earth metal halogen salts class is (as NaCl, KCl, Na
3alF
6deng)
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) in order to prevent material burning, the solution treatment carrying out within 470 ~ 560 DEG C, 30 hours to foundry goods is determined.
Compared with prior art, the present invention has following major advantage:
Solving the high tough aluminium alloy (ZL201A, ZL204A, ZL205A etc.) of current Al-Cu system adopts refined aluminium be matrix material and add the above noble element of thousandth mostly, cost is higher, cause the high tough aluminium alloy of Al-Cu system can only be used for the leading-edge field such as aerospace, defence and military, civil area applies limited problem because cost performance is not high.
Along with China and the quick growth of world aluminum output and aluminium industry size are in the continuous expansion of China, " 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 height that cost performance is high; The present invention is by adopting general aluminium to be matrix material, do not add (or adding less) noble element, preferred feature micro alloying element is filled a prescription, and adopt the techniques such as intensive, terse founding, purification, 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 requirements prerequisite, by Technology means such as thermal treatments, various strengthening phase fully, evenly, rationally being separated out and distribution in as-cast structure, makes 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 part of casting and structural part, also first can cast bar and carry out being hot extruded into the section bar into various section again.
In essence, this material belongs to the cast aluminium alloy of multicomponent microalloying, but has fabulous mobility and intergranular self-lubricating property due to material, makes it possess the easy processing characteristics of wrought aluminium alloy simultaneously.
3, the advance of technique.From production technique, smelting technique changes traditional extensive technique, electric furnace can be used to carry out tight protectiveness melting, thus avoid melt and be mixed into too much impurity and gas, both maintained the purity of alloy, and also simplified and shorten complicated subsequent melt treatment scheme; Meanwhile, fusion process substantially increases energy utilization rate compared with conventional reflective melting technology and reduces the pollution to environment, belongs to environment protecting and power-saving type technique.
(1) protectiveness melting significantly reduces energy consumption, pollution, simplifies Production Flow Chart, improves intensive degree
Because Al and Alalloy melt has extremely strong air-breathing tendency, thus melt in open type or the bad stove of closure and melting time, the aluminium alloy of melting can absorb the O in air in large quantities
2, the gas such as moisture, generate insoluble Al
2o
3with the H with excellent activity
2, form impurity and gas in the melt, if removed not in time, the slag inclusion of foundry goods, pore, the defect such as loose be formed when casting, causing goods to be scrapped; Wherein especially with H in melt
2harm maximum because H
2solubleness when solubleness when Al and Alalloy molten state is much higher than solid-state, therefore when solidifying, has a large amount of H
2from alloy, effusion causes a large amount of defect.Insoluble slag then relatively easily removes.Therefore, melt air-breathing is avoided to be the important measures keeping melt quality and castability.
Common large scale industry aluminum alloy smelting furnace is with liquid or geseous fuel be the energy reflector oven or holding furnace, needs a large amount of air-breathings, simultaneously in products of combustion containing a large amount of water vapor and CO
2, NO
xdeng material, at high temperature very easily with aluminium generation chemical reaction and generate various detrimental impurity, these impurity itself are the same with aluminium liquid simultaneously very easily adsorbs H
2, make melt be subject to severe contamination, before casting, the cleaning section that melt must experience together or a few road is special, and casting flow process of being allowed for access after sampling detection is qualified, this extends work flow undoubtedly, and energy consumption and contamination index are all difficult to reduce; Simultaneously because the continuity requirement of producing, equipment must be made to maximize, add investment, improve technique approval 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, seldom takes airtight sfgd. to aluminium alloy melt, causes melt quality and castability not high equally.
The preparation method of application claims, its melting mode is the Induction Heating Equipment adopting with closure, when having eradicated fuel combustion, air, water vapor and various products of combustion are to the pollution of melt, simultaneously in fusion process, protective gas can be adopted to carry out protective atmosphere melting, farthest the invasion and attack of isolated air; Owing to maintaining the high purity of melt, can take very simply by formula degasification, deslagging device in cast sections thereafter, and special stop formula soaking equipment need not be added, thus enormously simplify technical process.
(2) optimize the thermal treatment process of foundry goods, avoid the generation that material mechanical performance reduces, goods are scrapped caused 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 " less than 620 DEG C, within 72 hours ", in materials application test, when during discovery solution treatment, temperature surpasses 560 DEG C, usually can there is " burning " phenomenon, cause the destruction of material microstructure, its characteristic feature is that the leading indicator such as intensity and ductility significantly reduces, foundry goods becomes fragile, surface blackening shades, even namely crack in heat treatment process, be out of shape and scrap.And when solid solubility temperature is lower than 470 DEG C, because the cultivation of strengthening phase, precipitation strength effect are insufficient, the intensity of material is difficult to the target value reaching expectation; Meanwhile, after groping through test of many times, find that heat treatment time was more than 30 hours, did not have unusual effect to the raising of material property.Therefore, in order to improve effect and efficiency, heat treatment process parameter is optimized and revised into the solution treatment within 470 ~ 560 DEG C, 30 hours.
The science of 4, filling a prescription and economy.From raw material sources, advanced formula creates 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 (i.e. two zero aluminium, comprise aluminium liquid and remelting aluminium ingot), refined aluminium or high-purity grade of aluminium must be adopted to be the prescription model of matrix alloy than existing aldural, 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.On the other hand, the contribution rate raised because of noble element alloy cost is the tens of of common element and even more than hundred times, and in the alloying element combination of novel material series, majority does not adopt noble element, even if adopt, ratio is also very little, all below thousandth; And the ratio of existing aldural noble element is all more than thousandth, the advantage of two aspects is that serial novel material opens up a market and laid in great potential.
The present invention is by preferred alloy principal element copper (Cu), manganese (Mn) and the polynary formula that is feature micro alloying element with chromium (Cr), lithium (Li), for material base condition is created in the cultivation of high-temperature-phase in sosoloid and strengthening phase and grain refining effect, alloy forms strengthening θ phase (Al at principal element Cu, Mn
2cu), T-phase (Al
12mn
2cu), on basis, select high temperature elemental chromium (Cr), lithium (Li) and rare earth elements RE as the trace additives of complex alloys, Cr forms β-CrAl7, η-Cr in the alloy
25 kinds of dispersivity High-Temperature Strengthening phases such as Al, Li forms Al in the alloy
2li
3, AlLi
5deng 5 kinds of dispersivity High-Temperature Strengthening phases, heavy alloyed hardness and corrosion resisting property can be put forward; Rare earth elements RE can form various metals compound (as aluminium lanthanum has α-Al in aluminium alloy
11la
3, β-Al
11la
3, AlLa
3deng, aluminium cerium has α-Ce
3al
11, CeAl
3, CeAl
2deng, aluminium praseodymium has α-Al
11pr
3, ρ-AlPr
3deng, aluminium neodymium has α-Al
11nd
3, AlNd
3deng, aluminium promethium has Al
11pm
3, AlPm
2deng, aluminium samarium has Al
11sm
3, AlSm
2deng, aluminium europium has Al
4eu, AlEu etc., aluminium gadolinium has Al
4gd, Al
17gd
2deng, aluminium terbium has Al
3tb, AlTb
2deng, aluminium dysprosium has α-Al
3dy, AlDy
2deng, aluminium holmium has Al
3ho, AlHo
2deng, aluminium erbium has Al-Er:Al
3er, AlEr
2deng, aluminium thulium has Al
3tm, AlTm etc., aluminium ytterbium has Al
3yb, Al
2yb etc., aluminium lutetium has Al
3lu, AlLu
2deng, aluminium yttrium has Al
3y, AlY
2deng, aluminium scandium has Al
3sc, AlSc
2deng, total nearly hundred kinds of infusibility active metallic compounds), all significantly improve the room temperature strength of alloy, 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, comparatively Al-Cu system cast aluminium alloy cupric (Cu) amount be 3 ~ 11% scope slightly different, but in theory then there is earthshaking innovative significance.
On the one hand, when copper (Cu) content is 5.65 ~ 5.7%, just in time equal the eutectic solubleness of Cu in made of Al-Cu alloy, change according to the turn model of " precipitations-grain-boundary strengthening phase-brilliant gap weighting agent of complete solid solution-evenly (bond, inlay, anti-skidding) " and the mechanism of action in heat treatment process, form more rich Cu strengthening phase (comprising Al
2cu and θ phase), thus the room temperature of aluminium alloy and mechanical behavior under high temperature are improved all greatly, also improve processing characteristics, but sharply decline because the solubility with temperature of Cu in Al reduces, in crystallization and freezing process, the degree of supersaturation of Cu in α-Al sosoloid improves fast, α-Al dendrite is while grow up, strong tendency of discharging rich Cu strengthening phase outside crystal boundary with increasing 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 exceeding the instant actual strength of alloy, then form thermal crack, therefore in the certain limit of copper (Cu) content≤5.65%, the castability of aluminium alloy is the poorest, hot cracking tendency is maximum.But total trend is, along with the reduction of copper content, the hot cracking tendency of alloy also reduces; As 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, defect more between crystal boundary can be formed in the precipitation of crystal boundary with to dissolving in of intracrystalline when temperature variation, low-alloyed room temperature and hot strength are fallen, so Cu content is too low, concerning nonsensical simple made of Al-Cu alloy; If but in alloy, added more rare earth element (RE), then could play and make up the too low special-effect of Cu content.
On the other hand, when Cu content >=5.7%, rich Cu phase all can not be absorbed by matrix when thermal treatment, then with border rich Cu metallic compound form Dispersed precipitate in crystal boundary, reduce the concentration difference of Cu particle inside and outside α-Al sosoloid, in process of setting, mild α-Al sosoloid dendrite discharges the intensity of rich Cu phase to crystal boundary, namely reduces structural stress and hot cracking tendency.Obviously, when Cu content >=5.7%, rich Cu phase is more, during crystallization the structural stress of alloy inside and hot cracking tendency less; Meanwhile, the rich Cu phase of the thin brilliant disperse of high-melting-point forms active heterogeneous nucleus when melt crystallization, and accelerate melt crystallization reaction but stop nuclei growth, refinement crystal grain, also reduces Hot-Crack Tendency of Alloy; And make filling between matrix crystal boundary fuller; Rich Cu phase can also form refractory metal compound with the multiple element such as Al, Mn.All these effects, weaken the surface tension of melt significantly, reduce melt viscosity, thus significantly improve the castability of fluidity of molten and alloy.
When Cu content is in about 5.7%, after heat treatment, more rich Cu phase (dissolving in-precipitated phase) and the less thin brilliant disperse phase of (about 0.5%) Cu metal carbonyl compound is had at matrix crystal boundary, the alloy strength under room temperature state is made to keep higher level, but when being in hot environment, because a large amount of rich Cu phase is dissolved in matrix again, will cause more intercrystalline voids and defect, this can make the hot strength of alloy significantly decline.Along with Cu content continues to increase, the degree of alloy strength temperature influence reduces, and when disperse phase and precipitated phase are in equivalent state substantially, the strength of materials is acted upon by temperature changes minimum, and now in alloy, Cu content should be 11 ~ 12%.
But when in alloy during Cu content > 10%, Cu phase because of surplus during crystallization has 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, the excellent effect of original disperse phase to aluminum substrate phase is all shielded, and therefore 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 the MnAl that manganese (Mn) element and matrix effect generate
6with fine aluminium, there is identical current potential, effectively can improve corrosion stability and the weldability of alloy; Mn is as High-Temperature Strengthening phase simultaneously, has the effect improving recrystallization temperature, suppress recrystal grain alligatoring, can realize the solution strengthening of alloy, supplements strengthening, improve resistance toheat; Under grain-refining agent effect, can with the Al of Fe Element generation pelletizing shape
3(Fe, Mn), effectively eliminate the deleterious effect of Fe alloy, therefore the present invention can allow Fe content in wider scope (Fe≤0.5%), and the benefit brought like this is: realize general aluminium and replace refined aluminium, reduce costs, expand raw material sources and materials application field.
3. mainly micro alloying element based on rare earth RE is used, and its content range is large, reach as high as 5%, rare earth element degasification in the alloy, slagging-off, cleaning action, crystal grain thinning and metamorphism can be given full play to, 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 is very strong in activity, and have stronger avidity to oxygen, hydrogen, sulphur, nitrogen etc., its deoxidizing capacity exceedes 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, the aluminium alloy containing rare earth is easy to and the above-mentioned substance generation chemical reaction in aluminium liquid when melting, and reaction product is insoluble to aluminium and enters in slag, thus the gas content in alloy is reduced, and the tendency making alloy product produce pore and shrinkage porosite reduces greatly.
Rare earth element can significantly improve the mechanical property of alloy.Rare earth element can to form between stable refractory metal compound as Al in aluminium alloy
4rE, Al
8cuRE, Al
8mn
4rE, Al
24rE
3mn etc.Between these refractory metals, compound disperses is distributed in intergranular in netted or skeleton shape and interdendritic, and with matrix mortise, serve the effect of strengthening and stable crystal boundary.Meanwhile, in alloy, also form the AlSiRE phase of some amount, because its fusing point and hardness are very high, therefore to putting forward heavy alloyed thermotolerance and wear resistance all has good effect.In addition, also can in and molten metal in low melting point element Sn, Pb, Sb etc., form dystectic compound with them or make them be uniformly distributed in whole crystal from interdendritic, eliminate dendritic structure.
Rare earth element has crystal grain thinning and metamorphism.Rare earth element is surface active element, can integrated distribution on crystal boundary face, reduce melt viscosity, strengthen mobility, reduce pulling force between phase and phase because make the merit of formation critical size nucleus reduce, nuclei of crystallization quantity increase, thus make grain refining.The metamorphism of rare earth to aluminium alloy has long-lasting and remelting stability, and most of single or mishmetal adds has very strong refinement and metamorphism mutually afterwards to α-Al.
In addition, rare earth element can also put forward heavy alloyed electroconductibility.Due to rare earth energy refinement aluminium grain, also stable compound can be formed (as CeFe by the impurity such as Fe, Si in the alloy
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 (about 2%).
The rare earth elements RE of little amount alloy performance can produce significantly rotten improving effect, therefore, the rare earth adding quantity of general aluminium alloy is below 1%, in 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 patent applications, content of rare earth is defined as 0.05 ~ 0.3%.Analyze from Al-RE alloy phase diagram, due to the solubleness of most of rare earth in aluminium very little (as Ce is about 0.01%), its existing forms is distributed in crystal boundary or base intracrystalline portion mainly with compound between refractory metal.Because activity is very high, serve as scavenging agent and consume a part in cleaning molten, if add-on very little, then it is just difficult to give full play to the metamorphism of α-Al phase.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 spy considers copper content together with content of rare earth, determines that its content range is 0.05 ~ 5%.
4. chromium (Cr) element is as the feature Addition ofelements of complex alloys, can form β-CrAl in the alloy
7, η-Cr
25 kinds of dispersivity High-Temperature Strengthening phases such as Al, lithium (Li) element, as the feature Addition ofelements of complex alloys, can form Li in the alloy and form Al in the alloy
2li
3, AlLi
5deng 5 kinds of dispersivity High-Temperature Strengthening phases, heavy alloyed hardness and corrosion resisting property can be put forward.
5, excellent castability.By the foundry goods repeatedly foundry trial used in several field such as high-tech structure, Aeronautics and Astronautics, civilian heavy industry, demonstrate the excellent properties of this novel material: castability higher than current A201.0, ZL206, ZL207, ZL208, the high strength cast aluminum alloys such as 206.0, the significant problem that when solving the casting of above-mentioned aluminium alloy, hot cracking tendency is large, casting qualified rate is low; Old material melts down remelting and virgin material and can realize arbitrary proportion and prepare burden, new and old material blend melt casting performance is without change, and have the good action of stable material intensity, raising ductility, the situation that the reuse of more original aldural waste material is poor, circulation route is long, has extremely significant economy and intensivism.
The principle that hot cracking tendency eliminated by novel material is: form rich Cu phase because copper content in alloy increases, rich Cu phase as the thin brilliant disperse phase of high-melting-point with metallic compound form Dispersed precipitate in crystal boundary, the strong tendency to grain boundary decision that in crystal grain, rich Cu solute is formed because degree of supersaturation sharply raises effectively is counteracted when melt crystallization, thus structural stress when slow down crystallization; The simultaneously multiple disperse phase of the element such as rich Cu disperse phase and Cr, Li feature micro alloying element, RE microalloying of rare earth element and Mn, Zr, Ti, B on crystal boundary, all there is crystal grain thinning, filling matrix crystal boundary, form the multiple effect of nearly aluminium noble potential metal compound, all these effects weaken the surface tension of melt significantly, reduce melt viscosity, thus significantly improve the castability of fluidity of molten and alloy, ensure that cast article has higher qualification rate.
The principle that old material reuse is good is: in the present invention, multicomponent microalloying effect has long-lasting and remelting stability, during remelting, the structural performance of melt maintains atomic group structure and the fine crystalline structure of an alloy melt formation, a large amount of active nucleus can give full play to the effect of cohesion, assimilation microlitic structure in the melt, and can keep original mobility.Therefore, the good action allocated stable material intensity into, improve ductility of old material.
This characteristic of old material, can be implemented in the instant reuse of production scene completely, is no matter slag charge, processing clout or rejected casting, all can with virgin material together melting or directly add in melt.
This kind of characteristic of the present invention, the 1XXX system widely applied comparatively at present and 2XXX series high strength aluminum alloy materials qualified casting significantly improve, greatly reduce rejection number, therefore large waste product stockyard (in actual production, aluminium alloy molding floor often will cook up very large scrapground ground) is not needed in production scene; Meanwhile, a lot of cast aluminium alloy does not possess remelting stability, cannot direct reuse at the scene, therefore needs batching to focus on, occupies very large manufacturing cost, derive 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 surface anodization, thickness can reach standard-required grade, surface color without change, and the tack of coating and oxidized surface reaches the standard class that resistance to rupture is tested completely.
7, excellent high-temperature behavior.This material has the characteristic of high temperature aluminium alloys, under can reaching 400 DEG C of conditions, intensity is 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 the parts that aeroplane engine casing body directly bears high-temperature fuel gas calcination.(thermotolerance principle is see the content about copper-rich phase, rare earth RE, refractory alloy element Cr, Li etc. in characteristic 4 " science of formula and economy ").
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, therefore this serial novel material belonged to primitiveness, basic great innovation in the world.
Innovative point of the present invention
It is elementary composition that table one lists with close 31 kinds of aluminium alloys on the present invention's character and utilization in one aspect.Can find out, compared with existing various high copper content wrought aluminium alloy, heat-resistant deforming aluminium alloy, birmastic, the present invention mainly contains following innovative content.
One is that copper (Cu) content allowed band is large, 1 ~ 10%; Coordinate with manganese (Mn) element simultaneously and form multiple High-Temperature Strengthening phase.
Two is mainly use micro alloying element based on rare earth RE, and its content range is large, reach as high as 5%, rare earth RE degasification in the alloy, slagging-off, cleaning action, crystal grain thinning and metamorphism can be given full play to, 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, the effect of thus its deoxidation, desulfurization, removal hydrogen and nitrogen is all very strong, in addition, RE is surface active element, can integrated distribution on crystal boundary face, reduce pulling force between phase and phase, because make the merit of formation critical size nucleus reduce, nuclei of crystallization quantity increases, thus makes grain refining.
Three is comparatively loose to the restriction ratio of ferro element, allows that its content is maximum reaches 0.5%, and this has opened up space for using general aluminium for matrix carries out alloy material founding.
Four is do not use the low melting point element such as magnesium, zinc as the material producing strengthening phase, avoids decomposition and the conversion of material under high temperature strengthening phase, thus significantly improves the hot strength of material.
Five is the feature Addition ofelements using chromium (Cr) element as complex alloys, can form β-CrAl in the alloy
7, η-Cr
25 kinds of dispersivity High-Temperature Strengthening phases such as Al, lithium (Li) element, as the feature Addition ofelements of complex alloys, can form Al in the melt
2li
3, AlLi
5deng 5 kinds of dispersivity High-Temperature Strengthening phases, heavy alloyed hardness and corrosion resisting property can be put forward; Be combined titanium (Ti), boron (B), zirconium (Zr) element as comprehensive grain-refining agent, the basic substance of whole premium properties such as the heat-resisting and melt high workability of alloy material is possessed 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
The mechanical property of the present invention and existing several high tough aluminium alloy contrasts, in table two by applicant.
The mechanical property of table two the present invention and several high-toughness casting aluminum alloy
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.
3, high-temperature behavior
Applicant tests the intensity high temperature endurance performance of the present invention under all temps condition, and contrasts, in table three with the high temperature endurance performance of existing conventional heat-resisting aluminium alloy.
The height of table three the present invention and conventional heat-resisting aluminium alloy mixes enduring quality
As can be seen from Table III, room temperature strength of the present invention is greater than 450Mpa, and at more than 300Mpa during hot strength 250 DEG C, during hot strength 300 DEG C, 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, Cr-Li-RE High-strength heat-resistant aluminum alloy material of the present invention has high-tech content, the Application Areas of the length and breadth of land and splendid market outlook, its extremely excellent cost performance makes it can substitute current nearly all aldural and high temperature aluminium alloys, represents the developing direction of the light strong structured material of 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) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare-earth elements La again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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 element La and Ce mishmetal
(1) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element La and Ce mishmetal again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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) required various alloying elements are weighed by following charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element Eu again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element La and Ce, Pr mishmetal again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element er again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element nd again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element ce again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(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) required various alloying elements are weighed by charge calculation table, as follows.
(2) in smelting furnace, add appropriate aluminium ingot, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; For preventing melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) Al-Mn, Al-Ti, Al-Cr, Al-Li, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) is first added by formula rate again, Cu pure metal and Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth element y again, stir.
Hybrid metal additive refers to interpolation, the pie of adjustment alloy constituent element or block non-sintered sintered metal product, comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.Flux refers to the mixture of basic metal or alkaline earth metal halogen salts class, comprises NaCl, KCl and Na
3alF
6.
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating mode, and boron salt alterant etc.), and stir, simultaneously for preventing melt from sucking moisture content and scaling loss, melt refining should operate as far as possible in enclosed environment.
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment.
(6) (in the mould crystallization and freezing) is cast.
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods.
(8) sample index: tensile strength 487Mpa, unit elongation 4.3%.
Claims (6)
1. the preparation method of a Cr-Li-RE High-strength heat-resistant aluminum 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;
Its preparation method, comprises the steps:
(1) within the scope of above-mentioned element ratio, a selected group element ratio, the alloy total amount prepared as required again, extrapolate the quality of often 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 is incubated at 700 ~ 800 DEG C; Melting process completes in enclosed environment;
(3) Mn, Ti, Zr, Cr, Li pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Cr, Al-Li master alloy or hybrid metal additive is first added by formula rate again, Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive is added again after stirring, add B and rare earth elements RE again, stir;
(4) then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent, and stir, melt refining operates in enclosed environment;
(5) slag hitting after refining, leave standstill, temperature adjustment to 630 ~ 850 DEG C, aluminium alloy is toppled over and is come out of the stove, online degasification, except Slag treatment;
(6) cast;
(7) solution treatment within 470 ~ 560 DEG C, 30 hours is carried out to foundry goods;
Hybrid metal additive refers to interpolation, the pie adjusting alloy constituent element or block non-sintered sintered metal product.
2. the preparation method of Cr-Li-RE High-strength heat-resistant aluminum alloy material according to claim 1, is characterized in that: rare earth elements RE is Rare Earth Elements Determination or mishmetal.
3. the preparation method of Cr-Li-RE High-strength heat-resistant aluminum 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. the preparation method of Cr-Li-RE High-strength heat-resistant aluminum alloy material according to claim 1, is characterized in that: sintered metal product comprises manganese, copper, zirconium, chromium, lithium, boron or titanium metal powder and flux mixes.
5. the preparation method of Cr-Li-RE High-strength heat-resistant aluminum alloy material according to claim 4, is characterized in that: flux refers to the mixture of basic metal or alkaline earth metal halogen salts class.
6. the preparation method of Cr-Li-RE High-strength heat-resistant aluminum alloy material according to claim 1, is characterized in that: in step (4), and refining agent refers to chlorine, hexachloroethane, Manganous chloride tetrahydrate or boron salt alterant.
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| RU2785402C1 (en) * | 2022-06-10 | 2022-12-07 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | HEAT-RESISTANT CASTING AND DEFORMABLE ALUMINUM ALLOYS BASED ON Al-Cu-Yb AND Al-Cu-Gd SYSTEMS (OPTIONS) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2761567C2 (en) * | 2017-04-11 | 2021-12-10 | Зе Боинг Компани | Aluminum alloy with additives of copper, lithium and at least one alkaline earth or rear earth metal and its production method |
| RU2785402C1 (en) * | 2022-06-10 | 2022-12-07 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | HEAT-RESISTANT CASTING AND DEFORMABLE ALUMINUM ALLOYS BASED ON Al-Cu-Yb AND Al-Cu-Gd SYSTEMS (OPTIONS) |
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| CN102021378A (en) | 2011-04-20 |
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