CN102021388B - Ag-W-RE high-strength heat-resistant aluminium alloy material with C as modifier and preparation method thereof - Google Patents
Ag-W-RE high-strength heat-resistant aluminium alloy material with C as modifier and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Ag-W-RE high-strength heat-resistant aluminium alloy material with C as a modifier and a preparation method thereof. The aluminium alloy material 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, 0.0001-0.15% of C, 0.01-1.0% of Zr, 0.01-1.0% of Ag, 0.01-1.0% of W, 0.05-5% of RE and the balance Al. The invention finally develops the high-strength heat-resistant aluminium alloy material by taking the high-quality melt, solid solution and phase diagram theory as the guidance, giving preference to the main alloying elements Cu, Mn and RE as formulas, reducing the temperature range of the quasi-solid phase of the alloys, taking C as the efficient modifier, solving the problems of great hot cracking tendency, low high temperature strength of the products and the like during casting and giving preference to multiple microalloying elements as formulas.
Description
Technical field
The present invention relates to a kind of aluminum alloy materials and preparation method thereof, particularly a kind of Ag-W-RE high strength heat resistant alloy material rotten with C and preparation method thereof.
Background technology
Aluminium alloy is a kind of younger metallic substance, in 20 beginnings of the century, just starts industrial application.During World War II, aluminium is mainly for the manufacture of military aircraft.After the war, because the demand of war industry to aluminium die-offs, the aluminium industry member is just started to develop civil aluminum alloy, make its range of application expand to construction industry, container package industry, transportation, electric power and the each department of national economies such as electronic industry, machinery manufacturing industry and petrochemical complex by aircraft industry, be applied in the middle of 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 to wrought aluminium alloy and cast aluminium alloy two classes; The temperature condition that can use from goods is divided, and aldural is divided into again common aluminum alloy and high temperature (or heat-resisting) aluminium alloy.Up to the present, can meet the high strength at high temperature needs, only have the Al-Cu line aluminium alloy, from trade mark series, Al-Cu is associated gold and comprises cast aluminium alloy and wrought aluminium alloy, no matter and casting or be out of shape all belongs to 2 line aluminium alloys; And can meet the high-temp and high-strength aluminium alloy that good casting property is easily carried out deformation processing simultaneously, also do not see open the report.
1, high strength cast aluminum alloys and wrought aluminium alloy
General cast aluminium alloy comprises that AlSi system, AlCu system, AlMg system and AlZn are 4 series, wherein the intensity with AlCu system and AlZn line aluminium alloy is the highest, but most between 200Mpa～300Mpa, a few trade mark that only has AlCu system higher than 400Mpa, but, because adopting the refined aluminium matrix and adding noble element, manufacturing cost is very high; AlZn is that the resistance toheat of casting alloy is very poor.Therefore, general cast aluminium alloy is compared with wrought aluminium alloy because obdurability is slightly inferior and is made its range of application be subject to larger restriction.Many important use adopt wrought aluminium alloy as extraordinary traction engine bogie wheel, aviation alloyed aluminium etc., rather than cast aluminium alloy.Wrought aluminium alloy has reduced defect by means such as extruding, rolling, forgings, refinement crystal grain, improved density, thereby there is very high intensity, good toughness and good use properties.But high to the requirement of process equipment mould, operation is many, so the wrought aluminium alloy production cycle is long, cost is very high.Compare the plurality of advantages such as that cast aluminium alloy has is cheap, organize isotropy, can obtain special tissue, be easy to produce complex-shaped part, can small serial production also can produce in enormous quantities with wrought aluminium alloy.Therefore, develop can the Substitute For Partial wrought aluminium alloy high-toughness casting aluminum alloy material and casting forming process thereof, can reach the purpose of casting and forging, shortening manufacturing cycle, reduction manufacturing cost, there is important theory significance and great actual application value.
In the evolution of high-toughness casting aluminum alloy, the A-U5GT that France succeeded in developing in 20 beginnings of the century occupies an important position, in at present representative high-toughness casting aluminum alloy its history at most, be most widely used, China is the trade mark corresponding with it not at present; Transform on the A-U5GT basis behind the US aluminum association trade mark 201.0 (1986) and 206.0 (1967) and form, there is good mechanical property and stress corrosion resistant ability.
In the high-toughness casting aluminum alloy field, China has obtained the achievement of attracting attention in the world.The sixties, Beijing Research Inst. of Aeronautic Material succeeded in developing the ZL205A alloy to the seventies; ZL205A alloying constituent complexity, contain Cu, Mn, Zr, V, Cd, Ti, 7 kinds of alloying elements such as B; The tensile strength of ZL205A (T6) is 510MPa, is that the cast aluminium alloy material intensity of the existing registration trade mark at present is the highest; The obdurability of ZL205A (T5) is best, and unit elongation can reach 13%; But that the defect of ZL205A maximum is castability is poor, hot cracking tendency is large, simultaneously high because of formulation cost, 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, and the intergranular corrosion tendency is arranged.The qualified casting of this series alloy is very low.
In addition, 4 patent names that disclosed application number has been 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 be comprised of Cu, Mn, Ti, Cr, Cd, Zr, B and rare earth element, this aluminum alloy materials has higher tensile strength and unit elongation, tensile strength has reached 440Mpa, and unit elongation is greater than 6%; But this type of high-strength cast aluminium alloy material in use still fails to solve the particularly thorny of problem, alloy strength and castability that hot cracking tendency is large, its major cause is at alloy principal element Cu, Mn composition range, the accurate solid-state temperature a wider range of alloy, provide sufficient condition for thering is anisotropic dendrite growth during casting solidification, form powerful internal contraction stress solidifying the later stage, so it is large to shrink hot cracking tendency.
The 2XXX of official registration is that the wrought aluminium alloy trade mark has more than 70 at present, the overwhelming majority is U.S. Register, wherein only have 2001,2004,2011,14 trades mark such as 2011A, 2111,2219,2319,2419,2519,2021,2A16,2A17,2A20,2B16 be copper content at the high X alloy more than 5%, and wherein copper content is only having 2A16,2A17, these 4 trades mark of 2A20,2B16 more than 6%.All contain the compositions such as more Si, Mg, Zn in these wrought aluminium alloy formulas, and do not have rare earth (RE) etc. to play the element of Microalloying Effect, therefore its formula composition is that cast aluminium alloy differs greatly with 2, reflects different production technique and the deep processing technology of aluminium alloy of two kinds of attributes.
2, high temperature aluminium alloys
Superalloy claims again heat-resistance high-strength alloy, the strong alloy of heat or superalloy, it is a kind of important meals material grown up along with the appearance of aero-turbine in the forties in 20th century, can under high temperature oxidation atmosphere and exhaust gas corrosion condition, bear for a long time larger working load, being mainly used in the hot-end component of internal combustion turbine, is the important structure material of aerospace, naval vessel, generating, petrochemical complex and communications and transportation industry.Wherein some alloy also can be used for biotechnology and makes orthopaedics and dental material.
Superalloy commonly used comprises tungsten base, iron-based and cobalt base alloy, can under 600～1100 ℃ of hot environments, work; Heat-resisting aluminium alloy is to grow up during cold war.The heat-resistance high-strength aluminium alloy is suitable for bearing for a long time larger working load in the thermal environment below 400 ℃, in fields such as aerospace, heavy industry machineries, is more and more applied.Except the parts that aero-turbine, internal combustion turbine etc. directly contact with high-temperature fuel gas, all the other High Temperature High Pressure strong power parts all can adopt the casting of heat-resistance high-strength aluminium alloy.
Because the aluminium alloy ratio is easier to processing, along with the raising of processing technology level, in the situation that intensity meets the demands, people adopt wrought aluminium alloy to substitute cast aluminium alloy more and more.Therefore the heat-resistance high-strength aluminium alloy is divided into again Ajax alloy and the large class of alloy two for distortion.
In general, the heat-resistance high-strength alloy all contains multiple alloy element, many reach more than ten and plants.The element added plays respectively the effects such as solution strengthening, dispersion-strengthened, grain-boundary strengthening and surface stabilization in alloy, makes alloy can at high temperature keep high mechanical property and environmental performance.
The factor that should consider while selecting casting with superalloy:
(1) normal working temperature of foundry goods, the highest and minimum working temperature and the frequency of temperature variation.
(2) expansion character of the temperature range of foundry goods itself and alloy.
(3) load performance that foundry goods bears, 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.
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 at present, comprise aluminum bronze Mn series alloy and aluminium rare earth-based alloy; Wherein, aluminum bronze Mn series alloy majority be take high-purity grade of aluminium ingot as alloy material, and cost is higher, and at room temperature mechanical property is relatively poor for the aluminium rare earth-based alloy.And, at present heat-resistance high-strength aluminium alloy ubiquity hot strength low (more than 250 ℃, instantaneous tensile strength is less than 200Mpa, creep rupture strength is less than 100Mpa), formulation cost is high, castability is poor, casting qualified rate is low, waste product material and the defect such as the slag charge reuse is poor, causes the problems such as casting quality is poor, cost is high, the slag charge treatment scheme is long.In addition, also all contain noble element in the new formula of most heat-resisting aluminium alloy patents of declaring in recent years, and castability is poor, quality can't meet the requirement of aeronautical technology progress, is unsuitable for the industrialization production application.
And the heat-resistance high-strength wrought aluminium alloy that there is extensive use and the bright prospect of aurora in national economy and the modernization of national defense and development, in domestic and foreign literature, report is less, known 2219, 2A02, 2A04, 2A06, 2A10, 2A11, 2A12, 2A14, 2A16, 2A17, 2A50, 2A70, the 2XXX such as 2A80 are that the 7XXX such as wrought aluminium alloy and 7A04 are wrought aluminium alloy, at temperature more than 250 ℃, the intensity majority is less than 100Mpa, and its main alloy element is except Cu, outside Mn, all with Si, Mg, Zn is as main micro alloying element, and do not add this several elements, and more than 250 ℃ at temperature the heat-resistance high-strength wrought aluminium alloy material of intensity more than 150Mpa be not reported.
3, the rotten processing of aluminium alloy
The high materialization processing of melt is the core link of aluminium alloy smelting and pursues a goal, is basis and the prerequisite that obtains the fine aluminum alloy material simultaneously.High materialization is processed and is mainly comprised two aspects: the one, and sublimate, the 2nd, structural unit refinement and homogenizing.The former takes the method for an impurity solid state filtering and " with the gas degasification " to reduce melt impurity and hydrogen richness, and technological process can produce waste residue and waste gas; The latter is commonly referred to rotten the processing, be the size that makes to form the elementary cell xln of aluminium alloy melt and sosoloid with additive and/or machinery, physical method become as far as possible little, distribute even as far as possible, because additive enters alloy melt, become the effective ingredient of alloy, thereby do not produce waste residue and waste gas in process.It is the fundamental means of adjusting aluminium alloy as cast condition tissue that efficient alterant is particularly used in rotten processing.
According to the melt crystallization theory, the additive added as alterant should meet following requirement:
(1) at high temperature chemical composition is constant, and enough stability is arranged in molten aluminium;
(2) fusing point of additive should be than the height of aluminium;
(3) lattice of additive and aluminium should adapt on scantlings of the structure;
(4) form powerful adsorption bond with processed melt atom.
Generally adopt the processing of going bad of wire rod or pie additive at the wrought aluminium alloy Material Field at present, comprise titanium, boron, rare earth compound alterant etc., facts have proved, adopt suitable alterant to there is good improvement effect to the performance of wrought aluminium alloy material.And in the cast aluminium alloy field, the alterant adopted mostly is pulverous alkali metal halide composite salt, this type of alterant exist modification effect limited, increase foreign matter content in aluminium alloy, produce the shortcoming such as a large amount of obnoxious flavoures, realize having increased again trace elements in whole cleaning action in melt treatment, improved the environmental protection cost simultaneously.Usually, the alterant that the alkali metal halide composite salt is cast aluminium alloy as Al-Si has modification effect preferably, but is associated golden alterant as Al-Cu, and modification effect is inadequate.
In sum, the known problem existed in the research of heat-resistant high-strength field of aluminum alloys both at home and abroad at present has: lack rotten processing the efficiently in fusion process, hot strength and weather resistance deficiency, more than 250 ℃, high-temperature instantaneous intensity all is less than 250Mpa, and creep rupture strength all is less than 100Mpa; The materials processing poor performance; Waste disposal long flow path, cost are high, can't meet the requirement of aeronautical technology progress etc.
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, the goods yield rate is low, hot strength is low, the technical barriers such as waste product material and slag charge reuse are poor, with the high-quality melt, sosoloid and phase diagram theory are for instructing, using the C element as efficient alterant, by preferred alloy principal element Cu, Mn and rare earth element formula, reduce the accurate solid-state temperature scope of alloy, while solving casting, hot cracking tendency is 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 cultivation and the grain refining effect of high-temperature-phase in sosoloid and strengthening phase, and optimize melting, thermal treatment process technology, realize high-temperature-phase and the enough culture of strengthening phase and giving full play to of grain refining effect in sosoloid.The AlCu that finally develops a kind of rare earth multicomponent micro-alloying is novel high-strength heat-resisting (castibility and deformability) aluminum alloy materials.
Technical scheme of the present invention is, by weight percentage, this alloying constituent is Cu:1.0～10.0%, Mn:0.05～1.5%, Cd:0.01～0.5%, Ti:0.01～0.5%, C:0.0001～0.15%, Zr:0.01～1.0%, Ag:0.01～1.0%, W:0.01～1.0%, rare earth elements RE: 0.05～5%, all the other are Al.
Above-mentioned Ag-W-RE high strength heat resistant alloy material is characterized in that: rare earth elements RE is Rare Earth Elements Determination or more than one mixed rare-earth elements.
Above-mentioned Ag-W-RE high strength heat resistant alloy material, it is characterized in that: rare earth elements RE comprises La, Ce, Pr, Nd, Er and Y.
The preparation method of being somebody's turn to do the rotten Ag-W-RE high strength heat resistant alloy material with C comprises the steps:
(1) in above-mentioned element ratio scope, selected one group of feasible element ratio, the alloy total amount of preparing as required again, extrapolate the quality of every kind of required elemental metals, the perhaps quality of master alloy, perhaps the quality of hybrid metal additive (comprising salt compounds), work out the alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot.
(2) add appropriate aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Mn, Ti, Zr, Ag, W pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Ag, Al-W master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu, Cd pure metal or Al-Cu, Al-Cd master alloy or hybrid metal additive (comprising salt compounds) after stirring, add again C and rare earth elements RE, stir.
Wherein, the hybrid metal additive refers to 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, silver, tungsten or titanium metal powder and flux mix; Flux refers to that the mixture of basic metal or alkaline-earth metal halogen salt is (as NaCl, KCl, Na
3alF
6deng).C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7), in order to prevent the material burning, determine foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
Compared with prior art, the present invention has following major advantage:
Mostly to adopt refined aluminium be matrix material and add noble element to have solved current 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 for leading-edge fields such as aerospace, defence and militaries, and civil area is applied limited problem because cost performance is not high.
Along with the continuous expansion in China of China and the rapid growth of world aluminum output and aluminium industry size, " with aluminium for steel " day by day becomes trend and the trend of industry development, and at civil area the also high tough aluminium alloy of height in the urgent need to cost performance; The present invention is matrix material by adopting general aluminium, join and give a small amount of noble element, preferred feature micro alloying element formula, and adopt the techniques such as intensive, terse founding, purification, add efficient alterant, develop the novel high-strength heat-resistant aluminium alloy material, overcome the threshold on cost of current material.
Particularly, the present invention has following eight advantages.
1, high strength and high rigidity.From the strength of materials, require under prerequisite meeting plasticity, can be by Technology means such as thermal treatments, make various strengthening phases in as-cast structure fully, evenly, rationally separate out and distribute, make the strength of materials reach 480～540Mpa; Hardness >=HB140.
2, the double attribute of material.From the material applications attribute, it belongs to the both sexes aluminium alloy, the characteristic of existing cast aluminium alloy has again the characteristic of wrought aluminium alloy, both can be directly used in all kinds of light powerful parts of casting and structural part, also can first cast bar and is hot extruded into the section bar into various sections again.
In essence, this material belongs to the cast aluminium alloy of multicomponent microalloying, but, because material has fabulous mobility and intergranular self-lubricating property, makes it possess the easy processing characteristics of wrought aluminium alloy simultaneously.
3, the advance of technique.From production technique, changed traditional extensive technique on smelting technique, can use electric furnace to carry out tight protectiveness melting, thereby avoid melt to sneak into too much impurity and gas, the purity that had both kept alloy, also simplified and shortened complicated follow-up melt treatment flow process; Simultaneously, fusion process has greatly improved energy utilization rate and has reduced the pollution to environment than the conventional reflective melting technology, belongs to environment protecting and power-saving type technique.
(1) the protectiveness melting has significantly reduced energy consumption, pollution, has simplified Production Flow Chart, has improved intensive degree
Because aluminium and aluminium alloy melt have extremely strong air-breathing tendency, therefore melt in open type or the bad stove of closure and during melting, the aluminium alloy of melting can absorb airborne O in large quantities
2, the gas such as moisture, generate insoluble Al
2o
3with the H with excellent activity
2, form impurity and gas in melt, if remove not in time, can when casting, form the slag inclusion, pore of foundry goods, the defect such as loose, cause goods to be scrapped; Wherein especially with H in melt
2the harm maximum because H
2solubleness when aluminium and aluminium alloy molten state is much higher than solubleness when solid-state, therefore, when solidifying, has a large amount of H
2overflow and cause a large amount of defects from alloy.Insoluble slag is relatively easily removed.Therefore, avoiding melt air-breathing is the important measures that keep melt quality and castability.
Common large scale industry aluminum alloy smelting furnace is to take reflector oven or the holding furnace that liquid or geseous fuel be the energy, needs a large amount of air-breathings, contains a large amount of water vapors and CO in products of combustion simultaneously
2, NO
xdeng material, at high temperature very easily with aluminium generation chemical reaction, generate various detrimental impurity, simultaneously these impurity very easily adsorb H the same as aluminium liquid itself
2, make melt be subject to severe contamination, before being cast, melt must experience the special cleaning section in Huo Ji road one, and the casting flow process of being allowed for access after the sampling detection is qualified, and this has extended work flow undoubtedly, and energy consumption and contamination index all are difficult to reduce; Because the continuity requirement of producing must make equipment maximize, increase investment simultaneously, improved the technology access threshold; And the overhaul cost of equipment, start-up cost all are doubled and redoubled along with the maximization of equipment and long flow process.
And general aluminum alloy cast forging piece production plant, because production scale is little, equipment is simply extensive, and aluminium alloy melt is seldom taked to airtight sfgd., causes equally melt quality and castability not high.
The preparation method that the present invention requires, its melting mode is the Induction Heating Equipment that adopts with closure, air, water vapor and the various products of combustion pollution to melt while 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 isolated air; Due to the high purity that has kept melt, can take very simple through type degasification, deslagging device in cast sections thereafter, and needn't add special stop formula soaking equipment, thereby greatly simplify technical process.
(2) optimize the thermal treatment process of foundry goods, avoided the generation that material mechanical performance reduces, goods are scrapped caused 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 while finding solution treatment, temperature surpasses 560 ℃, " burning " phenomenon usually can occur, cause the destruction of material microstructure, its characteristic feature is that the leading indicators such as intensity and ductility significantly reduce, foundry goods becomes fragile, the surface blackening obfuscation, even in heat treatment process, crack, be out of shape and scrap.And when solid solubility temperature during lower than 470 ℃, because cultivation, the precipitation strength effect of strengthening phase are insufficient, the intensity of material is difficult to reach the target value of expectation; Simultaneously, after test of many times is groped, find that heat treatment time surpasses 30 hours, the raising of material property is not had to unusual effect.Therefore, in order to improve effect and efficiency, by heat treatment process parameter optimize and revise into: 470～560 ℃, 30 hours with interior solution treatment.
4, science and the economy of formula.From raw material sources, the matrix alloy of novel material series can adopt general industry fine aluminium (i.e. two zero aluminium, comprise aluminium liquid and remelting aluminium ingot), must adopt refined aluminium or the high-purity grade of prescription model that aluminium is matrix alloy than existing aldural, there is the advantages such as raw material supply abundance, cost is low, buying is convenient; Simultaneously, this material can adopt refined aluminium or high-purity grade of aluminium as matrix alloy equally, and the material of this formula has higher ductility than the general alumina-base material of this kind.
The present invention is by preferred alloy principal element copper (Cu), manganese (Mn), take the polynary formula that silver (Ag), tungsten (W) be the feature micro alloying element, for the cultivation of high-temperature-phase in sosoloid and strengthening phase and grain refining effect creation material base condition, (alloy principal element Cu, Mn form rich copper strengthening phase and (comprising: θ phase Al
2cu, T phase Al
12mn
2cu etc.); Take carbon (C) as the efficient alterant of alloy, due to the lattice parameter of the carbide formed close to the lattice parameter of aluminium sosoloid, these carbide particles group is as crystallization nuclei very tiny (its size is less than 1 μ m) and can stable existence in aluminium liquid under suitable refining temperature, in Casting Ingot Solidification Process, α-Al is had to fabulous stable refinement nucleation ability substantially, thereby make carbon alterant antidamping ability be better than other alterants, at utmost carry the heavy alloyed dispersity of organizing, realize best modification effect; Select high temperature elemental tungsten (W) and silver (Ag), the rare earth elements RE trace additives as complex alloys, W forms Al in alloy
12w, Al
6w, Al
43 kinds of dispersivity High-Temperature Strengthening phases such as W, put forward heavy alloyed hot strength; After adding a small amount of Ag element in alloy, promoted the formation of timeliness transition phase, improved the stability of GP district and transition phase, improved the alloy aging hardening characteristics, made alloy mechanical property obtain larger raising; Rare earth (RE) forms various metals compound dispersivity strengthening phase in alloy, and (for example: Rare-Earth Ce forms α-Ce in alloy
3al
11～β-Ce
37 kinds of metallic compounds such as Al; Rare earth La forms α-Al in alloy
11la
3～β l
11la
3deng 6 kinds of metallic compounds; Rare earth Pr forms α-Al in alloy
11pr
3～β-Al
11pr
3deng 6 kinds of metallic compounds; Rare earth Nd forms α-Al in alloy
11nd
3～β-Al
11nd
3deng 6 kinds of metallic compounds; Rare earth Er forms ErAl in alloy
3, ErAl
2, ErAl, Er
3al
2, Er
25 kinds of metallic compounds such as Al; Rare Earth Y forms Al in alloy
3y, Al
2y, AlY, Al
2y
3, AlY
2deng 5 kinds of metallic compounds; Rare earth Dy forms α-DyAl in alloy
3～β-DyAl
3deng 6 kinds of metallic compounds; Rare earth Eu forms EuAl in alloy
4, EuAl
2, 3 kinds of metallic compounds such as EuAl; Rare-earth Sm forms Al in alloy
11sm
3, Al
3sm, Al
2sm, AlSm, AlSm
2deng 5 kinds of metallic compounds; Rare earth Pm forms Al in alloy
11pm
3, AlPm
2deng 5 kinds of infusibility active metallic compounds; Rare-earth Gd forms Al in alloy
4gd, Al
17gd
2deng 7 kinds of infusibility active metallic compounds; Rare earth Tb forms Al in alloy
3tb, AlTb
2deng 5 kinds of infusibility active metallic compounds; Rare earth Ho forms Al in alloy
3ho, AlHo
2deng 5 kinds of infusibility active metallic compounds; Rare earth Tm forms Al in alloy
33 kinds of infusibility active metallic compounds such as Tm, AlTm; Rare Earth Y b forms Al in alloy
3yb, Al
22 kinds of infusibility active metallic compounds such as Yb; Rare earth Lu forms Al in alloy
3lu, AlLu
2deng 5 kinds of infusibility active metallic compounds etc.), all improved room temperature strength, high-temperature capability and the fluidity of molten of alloy.
The main alloying element mechanism of action of the present invention is as follows.
1. this material allows copper (Cu) content in 1～10% scope, is that cast aluminium alloy cupric (Cu) amount is 3～11% scope is slightly different than Al-Cu, but in theory has earthshaking innovative significance.
On the one hand, when copper (Cu) content is 5.65～5.7%, just in time equal the eutectic solubleness of Cu in the Al-Cu alloy, turn model and the mechanism of action according to " fully solid solution-evenly separate out-grain-boundary strengthening phase-brilliant gap weighting agent (bond, inlay, anti-skidding) " in heat treatment process change, and form more rich Cu strengthening phase (comprising Al
2cu, i.e. θ phase), thus the room temperature of aluminium alloy and mechanical behavior under high temperature are all improved greatly, also improved processing characteristics, but the solubility with temperature due to Cu in Al reduces and sharply descends, in the crystallization and freezing process, the degree of supersaturation of Cu in α-Al sosoloid improves fast, on one side α-Al dendrite is grown up, strongly increase the tendency of discharging rich Cu strengthening phase outside crystal boundary on one side, cause structural stress huge between intracrystalline and crystal boundary, alloy monolithic is in the solidification shrinkage stage simultaneously, string stress and structural stress are superimposed, when the instant actual strength that surpasses alloy, 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 defect between crystal boundary to dissolving in of intracrystalline at crystal boundary when temperature variation, low-alloyed room temperature and hot strength are fallen, so Cu content is too low, nonsensical concerning simple Al-Cu alloy; If but added more rare earth element (RE) in alloy, could play and make up the too low special-effect of Cu content.
On the other hand, when Cu content >=5.7%, rich Cu can not all be absorbed by matrix when thermal treatment, with border rich Cu metallic compound form disperse, be distributed in crystal boundary, reduced the concentration difference of the inside and outside Cu particle of α-Al sosoloid, in process of setting, mild α-Al sosoloid dendrite is discharged the intensity of rich Cu phase, has been reduced structural stress and hot cracking tendency to crystal boundary.Obviously, when Cu content >=5.7%, rich Cu is more mutually, and during crystallization, the structural stress of alloy inside and hot cracking tendency are less; Simultaneously, the rich Cu of the thin brilliant disperse of high-melting-point forms active heterogeneous nucleus when melt crystallization, accelerate the melt crystallization reaction but stop nuclei growth, refinement crystal grain, also reduced Hot-Crack Tendency of Alloy; And make between the matrix crystal boundary filling fuller; Rich Cu can also form the refractory metal compound with multiple elements such as Al, Mn mutually.All these act on, and have weakened significantly the surface tension of melt, have reduced melt viscosity, thereby have significantly improved the castability of fluidity of molten and alloy.
When Cu content during in 5.7% left and right, after heat treatment, at the matrix crystal boundary, more rich Cu phase (dissolving in-precipitated phase) and less (approximately 0.5%) the thin brilliant disperse phase of Cu based metallization compound are arranged, make the alloy strength under room temperature state keep higher level, but when in hot environment, because a large amount of rich Cu dissolve in matrix mutually again, will cause more intergranular space and defect, this can make the hot strength of alloy significantly descend.Along with Cu content continue to increase, the degree of alloy strength temperature influence reduces, and when disperse phase and precipitated phase during substantially in the equivalent state, it is minimum that the strength of materials is acted upon by temperature changes, and now in alloy, Cu content should be 11～12%.
But during Cu content in alloy>10%, during because of crystallization, the Cu of surplus has mutually preferential crystallization character and forms huge network structure, alloy viscosity strengthens greatly, surplus replaces the principal element that aluminum substrate becomes crystallization control in crystallisation process, original disperse phase is all shielded the good effect of aluminum substrate phase, so the various performances of alloy decline to a great extent again.
According to the checking of above theoretical basis and practice, determine that the zone of reasonableness of main alloying element Cu content is: 1～10% (wt%).
2. this material improves corrosion stability with manganese (Mn) element, shields impurity F e simultaneously, reduces the deleterious effect of Fe.
MnAl because of manganese (Mn) element and matrix effect generation
6there is identical current potential with fine aluminium, can effectively improve corrosion stability and the weldability of alloy; While, Mn was as the High-Temperature Strengthening phase, had the effect that improves recrystallization temperature, suppresses the recrystal grain alligatoring, can realize the solution strengthening of alloy, supplementary strengthening, raising resistance toheat; Under the grain-refining agent effect, can with the Al of Fe Element generation pelletizing shape
3(Fe, Mn), effectively eliminated the deleterious effect of Fe alloy, so the present invention can allow Fe content at wider scope (Fe≤0.5%), the benefit of bringing like this is: realize general aluminium substitution refined aluminium, reduce costs, enlarge raw material sources and material Application Areas.
3. mainly use rare earth RE as basic micro alloying element, and its content range is large, reach as high as 5%, can give full play to degasification, slagging-off, cleaning action, crystal grain thinning and the metamorphism of rare earth element in alloy, propose heavy alloyed mechanical property and solidity to corrosion effect.
The mechanism of rare earth element degasification, slagging-off, cleaning action is: the rare earth element activity is very strong, and oxygen, hydrogen, sulphur, nitrogen etc. are had to stronger avidity, and its deoxidizing capacity surpasses existing the strongest reductor--aluminium, can be content 50 * 10
-6oxygen, take off to 10 * 10
-6below, its desulfidation can be 20 * 10 measuring containing S
-6take off to 1～5 * 10
-6.Therefore, containing the aluminium alloy of rare earth when melting, be easy to aluminium liquid in above-mentioned substance generation chemical reaction, reaction product is insoluble to aluminium and enters in slag, thereby the gas content in alloy is reduced, the tendency that makes alloy product produce pore and shrinkage porosite reduces greatly.
Rare earth element can significantly improve the mechanical property of alloy.Rare earth element can form stable high melting point metal compound as Al in aluminium alloy
4rE, Al
8cuRE, Al
8mn
4rE, Al
24rE
3mn etc.These high melting point metal compound disperses are distributed in intergranular and the interdendritic that is netted or skeleton shape, and with the matrix mortise, played the effect of strengthening and stable crystal boundary.Simultaneously, also form the AlSiRE phase of some amount in alloy, due to its fusing point and hardness very high, therefore to putting forward heavy alloyed thermotolerance and wear resistance, good effect is all arranged.In addition, also can in and low melting point element Sn, Pb, Sb in molten metal etc., form dystectic compound with them or they be uniformly distributed in whole crystal from interdendritic, eliminated dendritic structure.
Rare earth element has crystal grain thinning and metamorphism.Rare earth element is surface active element, can concentrate and be distributed on the crystal boundary face, reduces melt viscosity, strengthens mobility, 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 of single or mishmetals add has very strong refinement and metamorphism mutually afterwards to α-Al.
In addition, rare earth element can also be put forward heavy alloyed electroconductibility.Due to rare earth energy refinement aluminium grain, also can in alloy, form stable compound (as CeFe by the impurity such as Fe, Si
5, CeSi, CeSi
2deng) and separate out from intracrystalline, add the cleaning action of rare earth alloy, make the resistivity of aluminium be reduced, electroconductibility improves (approximately 2%).
Seldom the rare earth elements RE of amount can the alloy performance produce significantly rotten improving effect, therefore, the rare earth adding quantity of general aluminium alloy is below 1%, in 200810302670.3,200810302668.6,200810302669.0 and 200810302671.8 patent applications, content of rare earth is defined as 0.05～0.3%.From the Al-RE alloy phase diagram, analyze, due to the solubleness of most of rare earth in aluminium very little (as Ce is about 0.01%), it exists form to be distributed in crystal boundary or base intracrystalline section mainly with high melting point metal compound.Because activity is very high, serve as scavenging agent and consume a part in cleaning molten, if add-on is very little, its metamorphism to α-Al phase just is difficult to give full play to.For keeping the long-lasting and remelting stability of RE Modified effect, and give full play to its High-Temperature Strengthening characteristic, the present invention is special to be considered copper content together with content of rare earth, determines that its content range is 0.05～5%.
4. tungsten (W) element adds element as the feature of complex alloys, and W forms Al in alloy
12w, Al
6w, Al
43 kinds of dispersivity High-Temperature Strengthening phases such as W, put forward heavy alloyed hot strength; Silver (Ag) element adds element as the feature of complex alloys, after adding a small amount of Ag element in alloy, promote the formation of timeliness transition phase, improved the stability of GP district and transition phase, improved the alloy aging hardening characteristics, made alloy mechanical property obtain larger raising.
5. take carbon (C) as the efficient alterant of alloy, due to the lattice parameter of the carbide formed close to the lattice parameter of aluminium sosoloid, these carbide particles group is as crystallization nuclei very tiny (its size is less than 1 μ m) and can stable existence in aluminium liquid under suitable refining temperature, in Casting Ingot Solidification Process, α-Al is had to fabulous stable refinement nucleation ability substantially, thereby do its antidamping ability of alterant with carbon and be better than other alterants, at utmost carry the heavy alloyed dispersity of organizing, realize best modification effect.
5, excellent castability.By the foundry goods that uses in the several fields such as high-tech structure, Aeronautics and Astronautics, civilian heavy industry foundry trial repeatedly, verified the excellent properties of this novel material: castability is higher than current A201.0, ZL206, ZL207, ZL208, the high strength cast aluminium alloys such as 206.0, the significant problem that while having solved above-mentioned aluminium alloy casting, hot cracking tendency is large, casting qualified rate is low; The present invention can be melted down remelting by old material, also can realize the arbitrary proportion batching with virgin material, new and old material blend melt casting performance is without change, and the good action that stable material intensity, raising ductility are arranged, the situation that the reuse of more original aldural waste material is poor, circulation route is long, have extremely significant economy and intensivism.
The principle that novel material is eliminated hot cracking tendency is: because copper content in alloy increases, form rich Cu phase, rich Cu is distributed in crystal boundary as the thin brilliant disperse phase of high-melting-point with the disperse of metallic compound form, effectively offset the strong tendency to the crystal boundary diffusion that in crystal grain, rich Cu solute forms because degree of supersaturation sharply raises when melt crystallization, thus the structural stress while having slowed down crystallization; The multiple disperse phase of rich Cu disperse phase and W, Ag feature micro alloying element, RE microalloying of rare earth element and Mn, Zr, the elements such as Ti, C on the while crystal boundary, all there is crystal grain thinning, filling matrix crystal boundary, form the multiple effect of nearly aluminium current potential metallic compound, all these effects have weakened the surface tension of melt significantly, reduced melt viscosity, thereby significantly improved the castability of fluidity of molten and alloy, made cast article there is higher qualification rate.
The good principle of old material reuse is: in the present invention, the multicomponent microalloying effect has long-lasting and remelting stability, during remelting, the structural performance of melt has kept atom bloc framework and the fine crystalline structure of an alloy melt formation, a large amount of active nucleus can be given full play to the effect of cohesion, assimilation microlitic structure in melt, and can keep original mobility.Therefore, the good action of allocating stable material intensity, raising ductility into of old material.
This specific character of old material, can realize the instant reuse in production scene fully, is no matter slag charge, processing clout or rejected casting, all can with together melting or directly add in melt of virgin material.
This specific character of the present invention, 1XXX system and the 2XXX series high strength aluminum alloy materials qualified casting widely applied at present significantly improve, greatly reduce rejection number, therefore do not need large waste product stockyard (in actual production, very large scrapground ground often will be cooked up in aluminium alloy casting workshop) in production scene; Existing a lot of cast aluminium alloys do not possess remelting stability simultaneously, and direct reuse, therefore need group batch to be focused at the scene, occupies very large manufacturing cost, derives a series of processing links and fruitless labour; And apply novel material provided by the invention, all these extra links, cost and fruitless labour all can be saved.
6, excellent processing, surface anticorrosion handling property.By novel material being processed into to the test of the finished parts of the different shapes such as axle, ball, pipe, angle section, bolt, testimonial material has fabulous processability, and surface can reach the fine and clean degree of nearly minute surface degree, and luminous reflectance factor is higher than fine aluminium; Surface oxidation and coated test show, after surperficial anodic oxidation, thickness can reach standard-required grade, surface color without change, and the tack of coating and oxidized surface reaches the standard class of resistance to rupture test fully.
7, excellent high-temperature behavior.This material has the characteristic of high temperature aluminium alloys, can reach under 400 ℃ of conditions intensity higher than more than 200Mpa, higher than traditional high temperature (heat-resisting) aluminum alloy materials, this characteristic makes novel material can substitute other each position heat-resistant part material except aircraft engine casket body directly bears the parts of high-temperature fuel gas calcination.(thermotolerance principle referring in characteristic 4 " science of formula and economy " about the content of copper-rich phase, rare earth RE, refractory alloy element W, Ag etc.).
8, typical original.This Novel series material is that the applicant develops fast after obtaining alloying theory innovation breakthrough, the checking of material excellent properties is exactly the checking to the new alloy theory simultaneously, and this theoretical breakthrough was not all clearly put down in writing at present on all documents and materials, so this series novel material belongs to primitiveness, basic great innovation in the world.
Innovative point of the present invention
Table one listed with performance in one aspect of the present invention and purposes on close 31 kinds of aluminium alloys elementary composition.Can find out, with existing various high copper content wrought aluminium alloies, heat-resistant deforming aluminium alloy, birmastic, compare, the present invention mainly contains following innovative content.
The one, copper (Cu) content allowed band is large, 1～10%; Coordinate and form multiple High-Temperature Strengthening phase with manganese (Mn) element simultaneously.
The 2nd, mainly use rare earth RE as basic micro alloying element, and its content range is large, reach as high as 5%, can give full play to degasification, slagging-off, cleaning action, crystal grain thinning and the metamorphism of rare earth RE in alloy, propose heavy alloyed mechanical property and solidity to corrosion effect; Rare earth elements RE is all very strong to the avidity of oxygen, sulphur, nitrogen, hydrogen, thereby the effect of its deoxidation, desulfurization, removal hydrogen and nitrogen is all very strong, in addition, RE is surface active element, can concentrate and be distributed on the crystal boundary face, reduce pulling force between phase and phase, because the merit that forms the critical size nucleus is reduced, nuclei of crystallization quantity increases, thereby makes grain refining.
The 3rd, looser to the restriction ratio of ferro element, allow its content maximum can reach 0.5%, this is for using general aluminium to open up space for the founding that matrix carries out alloy.
The 4th, do not use the low melting point elements such as magnesium, zinc as the material that produces strengthening phase, avoid decomposition and the conversion of material reinforcement phase under high temperature, thereby significantly improved the hot strength of material.
The 5th, the W element of usining adds element as the feature of complex alloys, and W forms Al in alloy
12w, Al
6w, Al
43 kinds of dispersivity High-Temperature Strengthening phases such as W, put forward heavy alloyed hot strength; Silver (Ag) element adds element as the feature of complex alloys, after adding a small amount of Ag element in alloy, promote the formation of timeliness transition phase, improved the stability of GP district and transition phase, improved the alloy aging hardening characteristics, made alloy mechanical property obtain larger raising.Be combined with titanium (Ti), zirconium (Zr) element as comprehensive grain-refining agent, alloy material is possessed whole basic substance of premium propertiess such as the heat-resisting and melt high workability of high-strength and high ductility.
The 6th, take carbon (C) as the efficient alterant of alloy, due to the lattice parameter of the carbide formed close to the lattice parameter of aluminium sosoloid, these carbide particles group is as crystallization nuclei very tiny (its size is less than 1 μ m) and can stable existence in aluminium liquid under suitable refining temperature, in Casting Ingot Solidification Process, α-Al is had to fabulous stable refinement nucleation ability substantially, thereby do its antidamping ability of alterant with carbon and be better than other alterants, at utmost carry the heavy alloyed dispersity of organizing, realize best modification effect.
More than the most obvious several 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 applicant is contrasted the present invention with the mechanical property of existing several high tough aluminium alloys, in Table two.
The mechanical property of table two the present invention and several high-toughness casting aluminum alloys
1. institute's column data is 206.0 high-purity alloys, i.e. W (Si)≤0.05%, W (Fe)≤0.10%.S-sand mold casting, J-permanent mold casting, R-investment cast
As can be seen from Table II, tensile strength 480～540MPa of the present invention, hardness is greater than HB140, obviously is better than the mechanical property of existing high tough aluminium alloy.
High-temperature behavior
The applicant to the present invention the intensity high temperature endurance performance under all temps condition test, and contrast with the high temperature endurance performance of existing commonly used heat-resisting aluminium alloy, in 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 during 250 ℃ of hot strengths, more than 300Mpa, during 300 ℃ of hot strengths, high temperature endurance performance is greater than 200Mpa, obviously is better than the high-temperature and durable of existing heat-resistance high-strength alloy.
In sum, the present invention be take the Ag-W-RE high strength heat resistant alloy material that C is efficient alterant and is had high-tech content and potential high-end applications field.
Embodiment
Embodiment 1:Cu-1.0%, feature micro alloying element-Ag, W, basic microalloying rare earth element-lanthanum La, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare-earth elements La, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 485Mpa, unit elongation 7.5%.
Embodiment 2:Cu-4.2%, feature micro alloying element-Ag, W, basic microalloying rare earth element La and Ce mishmetal, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth element La and Ce mishmetal, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 538Mpa, unit elongation 6.7%.
Embodiment 3:Cu-5.1%, feature micro alloying element-Ag, W, basic microalloying rare earth elements europium Eu, efficient alterant element-C
(1) by the good required various alloying elements of following charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth elements europium Eu, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 503Mpa, unit elongation 5.1%.
Embodiment 4:Cu-6.01%, feature micro alloying element-Ag, W, basic microalloying rare earth element-La, Ce, Pr mishmetal, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth element La and Ce, Pr mishmetal, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 533Mpa, unit elongation 4.1%
Embodiment 5:Cu-6.5%, feature micro alloying element-Ag, W, basic microalloying rare earth element er Er, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth element er, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 527Mpa, unit elongation 6.9%.
Embodiment 6:Cu-7%, feature micro alloying element-Ag, W, basic microalloying rear earth element nd Nd, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth element nd, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 517Mpa, unit elongation 5.3%.
Embodiment 7:Cu-8%, feature micro alloying element-Ag, W, basic microalloying rare-earth element cerium Ce, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth element ce, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 501Mpa, unit elongation 4.8%.
Embodiment 8:Cu-10%, feature micro alloying element-Ag, W, basic microalloying rare earth element yttrium Y, efficient alterant element-C
(1) by the good required various alloying elements of charge calculation table weighing, as follows.
(2) add appropriate aluminium ingot in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; For preventing that melt from sucking too much air, melting process should complete as far as possible at short notice with in enclosed environment.
(3) first add Al-Mn, Al-Ti, Al-Ag, Al-W, Al-Zr master alloy or hybrid metal additive (comprising salt compounds) by formula rate again, add again Cu pure metal and Al-Cd master alloy or hybrid metal additive after stirring, add again C and rare earth element y, stir.
The hybrid metal additive refers to interpolation, adjusts pie or block non-coking property sintered metal product that the alloy constituent element is used, comprises that manganese, copper, zirconium, silver, tungsten or titanium metal powder and flux mix.Flux refers to the mixture of basic metal or alkaline-earth metal halogen salt, comprises NaCl, KCl and Na
3alF
6.C refers to compound or aluminium carbon master alloy, comprises binary intermediate alloy, ternary master alloy and polynary master alloy.
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent (can adopt chlorine, hexachloroethane, Manganous chloride tetrahydrate etc. as refining agent according to different operating modes) in alloy melt, and stir, for preventing that melt from sucking moisture content and scaling loss, the melt refining should operate as far as possible in enclosed environment simultaneously.
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed.
(6) casting (crystallization and freezing in mold).
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
(8) sample index: tensile strength 487Mpa, unit elongation 3.9%.
Claims (4)
1. an Ag-W-RE high strength heat resistant alloy material rotten with C, it is characterized in that: by weight percentage, this alloying constituent is Cu:1.0～10.0%, Mn:0.05～1.5%, Cd:0.01～0.5%, Ti:0.01～0.5%, C:0.0001～0.15%, Zr:0.01～1.0%, Ag:0.01～1.0%, W:0.01～1.0%, rare earth elements RE: 0.05～5%, all the other are Al.
2. the Ag-W-RE high strength heat resistant alloy material rotten with C according to claim 1, it is characterized in that: rare earth elements RE is Rare Earth Elements Determination or mixed rare-earth elements.
One kind as claimed in claim 2 with C the preparation method of rotten Ag-W-RE high strength heat resistant alloy material, it is characterized in that: comprise the steps:
(1), in above-mentioned element ratio scope, a selected group element ratio, then the alloy total amount of preparation as required, extrapolate the quality of every kind of required elemental metals, or the quality of master alloy, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
(2) add appropriate aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt fully and insulation under 700～800 ℃; Melting process completes in enclosed environment;
(3) first add Mn, Ti, Zr, Ag, W pure metal or Al-Mn, Al-Ti, Al-Zr, Al-Ag, Al-W master alloy by formula rate again, add again Cu, Cd pure metal or Al-Cu, Al-Cd master alloy after stirring, add again C and rare earth elements RE, stir;
(4) then above-mentioned alloy melt is carried out to furnace refining; Add refining agent in alloy melt, and stir, the melt refining operates in enclosed environment;
(5) slag hitting after refining, standing, temperature adjustment to 630～850 ℃, aluminium alloy is toppled over and is come out of the stove, and online degasification, slagging-off are processed;
(6) casting;
(7) foundry goods is carried out to 470～560 ℃, 30 hours with interior solution treatment.
According to claim 3 with C the preparation method of rotten Ag-W-RE high strength heat resistant alloy material, it is characterized in that: in step (4), refining agent refers to chlorine, hexachloroethane or Manganous chloride tetrahydrate.
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