CN105937001A - Aluminum alloy material replacing QT600 wind turbine blade and forging forming method of aluminum alloy material - Google Patents
Aluminum alloy material replacing QT600 wind turbine blade and forging forming method of aluminum alloy material Download PDFInfo
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- CN105937001A CN105937001A CN201610492970.7A CN201610492970A CN105937001A CN 105937001 A CN105937001 A CN 105937001A CN 201610492970 A CN201610492970 A CN 201610492970A CN 105937001 A CN105937001 A CN 105937001A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
- C22C21/14—Alloys based on aluminium with copper as the next major constituent with silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/026—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/12—Alloys based on aluminium with copper as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/057—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with copper as the next major constituent
Abstract
The invention discloses an aluminum alloy material replacing a QT600 wind turbine blade. The aluminum alloy material is characterized by comprising the following main ingredients in percentages by weight: less than or equal to 2% of Mn, 0.05-0.5% of Cd, 4.2-8.0% of Cu, 0.12-0.20% of Zr and the balance of Al, wherein Cu is greater than or equal to 0.8Mn+ 4.05%; and the total quantity of a Lewis acid and base pair is 1%*10(-4)-2.0%, and therefore, the average grain size of alloy is smaller than 120 micrometers.
Description
Technical field
The present invention relates to a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator and preparation method thereof.
Background technology
Spheroidal graphite cast-iron (abbreviation magnesium iron) is widely used in manufacturing transmission case body, pump case, cylinder body, piston, wheel hub, driving member, part that tumbler equal strength high-wearing feature is good；Magnesium iron is the most of many uses, and also residing in it has the standard brand of segmentation, every kind of trade mark to define more strict accurate chemical composition combination, specification of heat treatment parameter, mechanical property and physical index etc., thus correspond to segmentation application category.It is shown in Table 1.
Mechanical property that the spheroidal graphite cast-iron trade mark that table 1 GB/T 1348 determines is corresponding and tissue
The mechanical performance index of magnesium iron and classification thereof, can as aluminum alloy materials innovative design, carry high performance to mark basis, can simultaneously serve as the comparison passage of " with aluminum for steel ", that is: if aluminium alloy can substitute certain trade mark magnesium iron, then substitute the steel close with this trade mark performance further, just be enough to lead a kind of trend or fashion in industrial circle.Realize substituting the strong structure of weight with light strong structure.
From the perspective of natural characteristic and experience accumulation, aluminium alloy has a multiple advantage compared with magnesium iron:
1. aluminum has fabulous cryogenic property, having unique advantage at low temperature environment as structural material, magnesium iron then reduces with temperature and gradually occurs by toughness to the transformation of fragility, especially below brittle transition temperature, its impact resistance drastically declines, and even " low-temperature brittle fracture " occurs.
2. aluminium alloy specific strength is high, has good fracture toughness (weighing the drag of metal material expansion unexpected to crackle), and magnesium iron counter stress concentrates sensitivity strong, can cause fracture suddenly.
3. due to aluminum and aluminium alloy are nonmagnetic substance thus electromagnetism interference performance is good, and magnesium iron is all good magnetic material within the temperature range of biological existence, easily by electromagnetic interference.
4. the corrosion resistance of aluminium alloy itself significantly larger than iron and steel and be more suitable for carrying out high-tech surface anticorrosion and decoration integrated process.
5. aluminium alloy is to the wettability of water well below iron and steel, thus low temperature sleety weather aluminum surface will not be susceptible to sleet ice attached weightening finish phenomenon as steel surface.
6. aluminum alloying and Technology for Heating Processing are simple compared with magnesium iron and steel, the alloying temperature of aluminum is generally below 750 DEG C, heat treatment temperature is between 150～600 DEG C, and bulb ferroalloy temperature is more than 1400 DEG C, heat treatment temperature, then at 500～1000 DEG C, consumes and discharge is aluminum several times or even more than ten times.
7. comparing from processing technique, aluminum can obtain the part of complicated shape or section easily, and needs more operation and equipment can consume more higher power than aluminum with the part of magnesium iron this complexity of processing.
8. aluminium alloy is less than magnesium iron inertia, equips more advantage frequently in start and stop.
These steel aforementioned shortcoming and the unique superior quality of aluminum, the marked improvement for " with aluminum for steel " provides the basis of reality that civilization of human society progress is pursued.
In the technology upgrading of " with aluminum for steel ", in order to give full play to aluminium alloy with " gently " advantageous characteristic as representative, it is necessary to make its aspect in " by force " have tremendous development, could significantly expand its use field.This just requires first to make a breakthrough in Al-alloy material design.
The method close examination prepared from material, material behavior is obtained by functional microcosmic thing is combined, need to obtain good functional thing combined, such as high intensity, high-ductility, high rigidity, corrosion-resistant etc., it it is the final result of various preparation method pursuit, therefore there is close internal integrity in the Design of Chemical Composition of aluminium alloy and its technology of preparing, is a kind of atom relation of how being combined into required " thing phase molecule ".Aluminium alloy each formula element is the major contributing link forming material thing phase molecule combinative structure by melting mixing, after process of setting, crystal grain determines crystalline state combination (submicron particles: about yardstick 10～300 μm) of alloy mutually with the intermetallic compound molecule thing of crystal boundary, and subsequent heat treatment is to fine structure under crystalline state group frame (micron particles: about yardstick 1～30 μm) or even precise and tiny structure (Subnano-class or the sub-micron grade particle: yardstick 10nm～＜ 1 μm=be adjusted and perfect of more microcosmic.
On engineer applied, on aluminium alloy grain size and shape and crystal boundary, the size shape of metallic compound, has conclusive impact to the mechanical property of alloy.Irregular crystals such as thick plane crystalline substance, dendrite, column crystal and be distributed in the thick brittle property intermetallic compound of crystal boundary, the obdurability contribution of matrix all can be balanced out by fine structure good for alloy and precise and tiny structure, the most conventional rotten means and the means of crystal grain thinning, best effect can only make mean grain size refine to 120～150 microns, and the form of dendrite does not often have basic transformation, this is the important bottleneck problem that alloy mechanical property improves further.Improve for enabling aluminum alloy to obtain intensity and toughness simultaneously, only carry out refinement and the rounding of crystal grain, refine the most further and the mean grain size of rounding alloy, be the target pursued all the time of industrial circle.
Analyze by aluminum bronze manganese systems (Al-Cu-Mn) alloy being up to spherical aberration correction scanning transmission electron microscope (STEM) the precise and tiny constituency of the very high resolution of 0.08nm, it is thus achieved that set up various phase structures on an atomic scale, Atomic Resolution and chemical element distribution.Confirm wherein to there is a series of hardening constituent, including well-known Al-Cu binary metastable phase (GP district, θ ＂, θ ＇), new disc phase and balance phase θ (Al2Cu)；Wherein inside matrix grain, new discovery one rod forked (T+ θ H) combination phase, the trunk portion T-phase of this combination phase is Al-Cu-Mn ternary phase, molecular structural formula Al20Cu2Mn3, molecule phase character be diameter about 100nm, length about 600～1000nm be mandrel shape and its (010) face and alloy matrix aluminum { 010} face coherence；And apposition growth size is compared with the Al-Cu binary secondary phase of big (thickness about 20nm, be about 50nm) around T-phase, owing to this secondary phase compares with other Al-Cu metastable phase in matrix (GP district, θ ＂, θ ＇ or other disc phase), structurally there is very big difference, particularly thickness is thicker much than other Al-Cu metastable phase, therefore the present invention is referred to as θ H phase, its molecular structural formula AlxCu (x is likely less than 2), is a kind of rich Cu molecule.
Theoretical according to alloy strengthening, the intensity of alloy is embodied in interface or dislocation movement by slip is hindered by particle, hinders intensity the biggest, walks around that particle leaves dislocation ring and to continue the obstruction of sliding the strongest.For aluminum bronze manganese systems (Al-Cu-Mn) alloy, the Al-Cu Binary-phase in GP district is the main intensifying factor of alloy, along with the binary Al-Cu metastable phase of θ ＂, θ ＇ or other disc shaped is grown up, when disc is big to a certain extent (more than 150nm, thickness only has 1～3nm to diameter), play maximum and hinder dislocation movement by slip ability, the contribution bigger to the elongation percentage holding of matrix.
As it was previously stated, the blade of wind-driven generator that tradition magnesium iron (QT600) makes, actual manufacture, use during there is following defect:
1. relatively low because of magnesium iron elongation percentage, the sensitivity that counter stress is concentrated substantially increases, and deforms after showing as surrendering
Measure less easy fracture, cause the accident.
2. magnesium iron heat treatment process is complicated, equipment technology requirement is high, and consumes and discharge the biggest.
3. along the whole life cycle of parts application, magnesium iron is higher than because of the defects such as big, heavy, perishable, the easy brittle failure of its inertia, its material consumption, energy consumption and maintenance cost very much, and its value recycled is relatively low.
Aluminium alloy blade of wind-driven generator has no correlational study at home, because the limitation of common aluminum alloy basic material, its mechanical property is relatively low, especially high-temperature heat-resistance performance, and the temperature born is less than 300 DEG C, has a strong impact on the life-span, even adds security risk.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator and preparation method thereof is provided, wherein add Lewis Acids and Bases pair, effectively expedite the emergence of critical nucleus (obtaining equiax crystal), alloy is made to obtain the optimal combined structure of molecule thing ((T+ θ H) combines phase) before curing, promote alloy crystalline state optimization, enable aluminum alloy to base material and realize 600Mpa and higher strength grade, thus reach to produce the Al-alloy products substituting QT600 blade of wind-driven generator.
The technical scheme is that: a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator, main constituent content by weight percentage: manganese Mn :≤2%, cadmium Cd:0.05%～0.5%, copper Cu:4.2%～8.0% and Cu >=0.8Mn+4.05%, zirconium Zr:0.12%～0.20%；Lewis Acids and Bases is to total amount 1% × 10-4～2.0%, making alloy mean grain size ＜ 120 microns, surplus is aluminum Al.
Described alloy grain is equiax crystal.
In described alloy grain, sub-nanometer (T+ θ H) combination phase amount reaches >=1/square micron.
Described Lewis Acids and Bases mixes for one or more in metallic hydrogen compound, metal halogen compound, main group dvielement.
Described metal halogen compound: include four chloro cobalt anion body [CoCl4]2 -。
Described metal halogen compound, including beryllium hydride BeH2。
Described Lewis Acids and Bases pair, accounts for Al matrix percentage by weight by element addition, and scope is: 0.4% ＜ Si ＜ 1.6%, BeH2＜ 0.11%, W ＜ 0.1%, [CoCl4]2 -＜ 0.1%.
The preparation method of a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator, comprises the steps of
(1) in the range of aforementioned Lewis Acids and Bases is to, element ratio, selected one group of combinations of substances, determine weight ratio, the alloy total amount prepared as required, extrapolate the weight of every kind of required material；
(2) adding aluminium ingot or molten aluminum liquid in smelting furnace, heating is also incubated more than 700 DEG C；
(3) addition manganese Mn, cadmium Cd, copper Cu, zirconium Zr stir, and add selected Lewis Acids and Bases pair, or the Lewis Acids and Bases that addition is selected is to combination, stirs；
(4) then above-mentioned alloy melt is carried out furnace refining；
(5) remove the gred after refine, stand, sample analysis alloy composition, adjust chemical composition in the deviation range of regulation according to analysis result；Homoiothermic is to more than 650 DEG C, and aluminium alloy is come out of the stove, online degasification, slagging-off；
(6) hot top casting: aluminium alloy is cast as pole；
(7) forging molding: pole forged one-tenth blade blank.
Described hot top casts, and step is as follows:
(1) chute and shunting disk are preheating to suitable temperature；
(2) melt proceeds to shunting disk from holding furnace through chute；
(3) opening cooling water, start casting machine, dummy bar head moves down；
(4) adjusting casting speed 80-140 mm/min, dummy bar head moves down along vertical shaft, and melt flows into crystallizer coagulation forming by chute and shunting disk；
(5) stop casting machine after having cast, close cooling water；
(6) dig shunting disk and hang out aluminium bar, be incorporated to stove homogenizing.
Described forging molding, step is as follows:
(1) upper and lower mould is preheating to suitable temperature；
(2) heating aluminium bar >=400 DEG C, and put into lower mold；
(3) aluminium bar is made to take out cooling after Deformation Flow full mould in mould by pressure；
(4) appearance quality detection: size, crackle；
(5) solution treatment: forge piece is sent into solid solution furnace, carries out less than 550 DEG C solution treatment, enters water quenching after being incubated at once；
(6) ageing strengthening: the goods completing solution treatment are sent into aging furnace and carries out ageing strengthening process, ageing strengthening below 230 DEG C, natural cooling of coming out of the stove after insulation；
(7) sample analysis test checking；
(8) Practical Performance checking.
Beneficial effects of the present invention: by using lewis' theory of acids and bases, Lewis Acids and Bases is made to occur to disintegrate and convert at aluminium alloy melt environment, to provide abundant disturbance and the activation effect of (0.1nm～10nm range scale) in the hyperfine microcell of melt, reach to expedite the emergence of critical nucleus to be formed in a large number, alloy grain degree is made to be refined further, shape more rounding；Optimize simultaneously very small areas (micron order: about yardstick 1～30 μm) and precise and tiny region (Subnano-class or sub-micron grade particle: yardstick 10nm～＜ 1 μm=thing phase molecule combinative structure, increase (T+ θ H) combination content in alloy substrate, enable aluminum alloy to matrix strength and obtain big lifting, it is well controlled between 400～600Mpa in yield strength, this is the engineer applied problem that the invention solves the problems that, i.e. alternate series ductile iron material and goods.
Cation body and anion body are as Louis " acid-base pair ", the hot environment of aluminium alloy melt is decomposed, generate lewis acid and lewis base, 1. the incipient bubble only one of which molecular size of gaseous material formation of release is decomposed under high temperature (less than 1nm, i.e. secondary nanophase), specific surface area is maximum, there is the disturbance ability of extremely strong activity and nanometer range, in causing melt superfinishing microcell, nuclear energy rises and falls, structure rises and falls and composition fluctuations, neighbouring more polyatom is promoted to cross over crystallization potential barrier, form a large amount of critical nucleus, it is better than the effect of common alterant such as aluminum titanium boron；Positive and negative ion body disturbance and activation effect in the superfinishing microcell of secondary nanometer range simultaneously, conventional additional purification bubble (diameter is more than 0.5mm) cannot realize；2. the metallic atom or the cation that decompose release have the volume less than part and bigger specific surface area, it is higher to disturbance and the activation effect of neighboring atom, the superfinishing microcell state caused rises and falls more significantly, the most higher to intermetallic compound reaction of formation catalysis and alloy substrate tissue Grain Refinement Effect；3. acid-base pair division in high-temperature fusant and reconstruct enhance the particle diffusion velocity at microcell, and restrained effectively the alloying component segregation and the gathering of bulky grain particle caused because of additive and grow up, and can prevent the roughening of titanium Ti and rare-earth phase；4. after part bubble occurs secondary reaction, purifying gas through a series of changes and discharge melt or enter slag, its purification is more preferable than conventional gas purification mode effect.By this mechanism, making matrix crystalline state generally become equiax crystal, grain size is averagely less than 120 μm, and further effect of optimization can reach grain size averagely in 50～100 μm.
In alloy melt, different metal atom or ion close, also can produce energy level splitting generation thermal chemical reaction (electron transfer does not occur) between them and form the pattern of intermetallic compound, according to electronegativity size, AlxCu and Al20Cu2Mn3Louis's " acid-base pair " can be regarded as.When the external Lewis Acids and Bases added in melt is to when decomposing, the intermetallic compound presoma that can differ from matrix Presence of an interface is the most also disturbed and activates and recurring structure fluctuating, produce more critical nucleus, make (T+ θ H) combination concentration mutually the most in the alloy and be evenly distributed density, make up to 1/[μm]2Above, here it is Lewis Acids and Bases can increase Subnano-class particle (T+ θ H) combination phase and nanoscale particle GP district, θ ＂, the mechanism of θ ＇ tandem reinforcement phase to disturbance and the activation effect at nanoscale.
Aluminium alloy melt is overall as a rich, high temperature electron system, electronegativity is higher than to its metallic element, it it is electron donor, and electronegativity is less than to its active metal element, it it is again electron acceptor, visible aluminium alloy melt also has the general general character of Lewis Acids and Bases, itself and the element added among it, also broad sense " Lewis Acids and Bases to " can be formed, therefore, can be the various elements adjusting melt chemistry activity, unified " lewis acid " or " lewis base " being considered as aluminium alloy, as the main group dvielement such as Mg using the present invention to provide, during interior transition dvielement such as Ce, in order to simplify description, and also to the prominent optimization function to aluminium alloy melt, individual element is also referred to as " Lewis Acids and Bases to ".
For aluminium alloy melt, the halogen compound such as [CoCl of metal4]2-With hydrogen peroxide adduct such as BeH2Combine with covalent bond between its atom, there is the feature of Lewis Acids and Bases pair, these the most sufficiently stable and particularly preferred materials of thermostability, after blowing into melt dispersedly with nanomorphic powder, due to high temperature, electron rich and the biggest specific surface area, the interface energy of generation be enough to cause material molecule to occur polarization deformation or even disproportionation to decompose, also disturbance and activation effect can be caused in nanometer range, it is also possible to be attributed to " Lewis Acids and Bases to ".
To sum up, Lewis Acids and Bases pair of the present invention, variform can be shown as, one or more in the negative ions body that is combined into part including metal, metal halogen compound, metallic hydrogen compound main group dvielement, interior transition dvielement mix.
Additionally, due to foreign peoples's material concentration that Lewis Acids and Bases is bigger to being supplied to alloy melt, therefore the constitutional supercooling degree of melt crystallization process is increased, nucleus is caused quickly to cross critical dimension under higher crystallization power, and free nucleation and growth in supercool liquid, formed and there is isotropism and shape closer to spherical equi-axed crystal；This because of the free growing endogenetic forming mechanism of liquid internal due to equiax crystal, change the irregular crystals such as plane crystalline substance, dendrite, column crystal because of the raw core of type wall of casting mold cavity, from the unidirectionally extended growth pattern of export-oriented liquid internal, therefore avoid or alleviate the component segregation of alloy, crystallize thick unidirectional, defect that macro property is uneven, thus it is prevented effectively from or alleviates some common deficiencies of alloy, such as pin hole, pore, shrinkage cavity and porosity, segregation, thick solid solution, high hardness compound, crackle etc..
The present invention is based on to the contrast image of alloy microstructure very high resolution and the structural analysis of precise and tiny constituency, it was found that intracrystalline also exists the hyperfine structure of (T+ θ H) excellent forked combination phase of sub-micron grade.Binary-phase each with Al-Cu compares, and (T+ θ H) combination has many advantages mutually, including: particle size is big, and anti-dislocation movement by slip face is big；Trunk portion T is the bar-shaped twin of high hard high stable compound polymerization, it is possible to walks around mode with dislocation and provides strength support for alloy；Its secondary θ H attachment on trunk oblique or be perpendicular to T mandrel direction and to surrounding matrix grows while with matrix coherence, enhance trunk and lattice dot matrix around is tightened up ability, or in other words, T mandrel is by adhering on it to the secondary phase of θ H of surrounding growth, tightening up the transmission of effect peripherad matrix space and diffusion, this act on time um region in matrix is created steel grid invigoration effect (can be described as " class concrete reinforced structure ") in concrete in similar building structure, make matrix strength be greatly improved.This effect, if compared from monomer, be in matrix flake Al-Cu metastable phase (GP district, θ ＂, θ ＇ or other disc phase) or a combination thereof all far from comparing；But, in common aluminum bronze manganese systems (Al-Cu-Mn) alloy, owing to each binary Al-Cu metastable phase is in the distribution density of distribution density significantly larger than (T+ θ H) combination phase of intrinsic silicon, the effect of (T+ θ H) combination phase is caused to be blanked and be never found.
(T+ θ H) combination optimizes the thing phase molecule combinative structure of aluminum bronze manganese systems (Al-Cu-Mn) alloy mutually, provides walking around strengthening effect and cutting through strengthening effect two kinds effect higher than what free state Al-Cu metastable phase combined of high Hard Inclusion T-phase for matrix；So the combination of Al-Cu metastable phase is transferred out merely from tradition by emphasis design of material must paid close attention to, and concentrates on and (T+ θ H) combination phase is expedited the emergence of in effect.
Inventive formulation is configured as one of technical way, is that the crystalline state combination making alloy realizes under the equiax crystal premise of mean grain size ＜ 120 microns, also can realize alloy grain internal (T+ θ H) combination phase amount 1/[μm]2Above.Therefore main constituent is designed as by weight percentage: manganese Mn :≤2%, cadmium Cd:0.05%～0.5%, copper Cu:4.2%～8.0% and Cu >=0.8Mn+4.05%, zirconium Zr:0.12%～0.20%；Lewis Acids and Bases is to total amount 1% × 10-4～2.0%, making alloy mean grain size ＜ 120 microns, surplus is aluminum Al, zirconium Zr energy crystal grain thinning, and puies forward the stability of heavy alloyed recrystallization temperature and solid solution, thus carries heavy alloyed thermostability, and improves the weldability of alloy and the plasticity of weld seam.
The result obtained by DSC differentia scanning calorimetry, the difference of the temperature range high lower bound that the chemical calorific effect of aluminum bronze manganese systems (Al-Cu-Mn) alloy occurs has 100 DEG C, in Al-Cu binary is each mutually, the Al of equilibrium state2The fusing point of Cu (θ) phase eutectic is up to 548 DEG C, is in the temperature position starting to occur heat effect on DSC curve, and when temperature is at 648.5 DEG C, heat effect is maximum, just without chemical calorific effect after temperature is higher.Rationally infer and the matrix coherence (T+ θ H) of this situation combine the endothermic thermal event melting (matrix melts simultaneously) mutually and cause.
The trunk T-phase of (T+ θ H) combination phase substantially increases thermostability and the calorific intensity of alloy；And (T+ θ H) combination phase amount and the raising of distribution density, improve the intensity of alloy, hardness and elongation percentage the most simultaneously.
Theoretical according to metal freezing, in terms of macroscopic perspective, a large amount of formation of critical nucleus needs the atom to being in free state in melt to reduce potential energy threshold to " jump " of lattice dot matrix ordered state, and this low threshold comes from two conditions: one is that the surface tension reducing liquid metal makes original nucleus easily spread and easily absorbs the atom of free state around, a kind of form creates the heterogeneous crystallization nuclei of stable state as much as possible exactly.
According to lewis' theory of acids and bases, aluminum melt is an electron rich high temperature system, i.e. belong to strong lewis base, after the copper manganese of excess adds, owing to the electronegativity of copper manganese is relatively strong, the more electron cloud of suction, make the alkalescence reduction of the alloy melt of formation, surface tension increases, and is unfavorable for the generation of critical nucleus；After adding electron rich material, balance the acid effect of copper manganese, the interfacial tension that original nucleus faces reduces, thus the original nucleus promoting the trunk T-phase of (T+ θ H) combination phase grows into critical nucleus, thus quantity and distribution density significantly improve in the alloy mutually to determine (T+ θ H) combination.
Detailed description of the invention
The specific embodiment of the invention includes 2 parts, and Part I is prompting and explanation, and Part II is specific embodiment.
Part I: point out and illustrate
The step that alloy melt prepares:
(1) in the range of aforementioned Lewis Acids and Bases is to, element ratio, selected one group of combinations of substances, determine weight ratio, the alloy total amount prepared as required, extrapolate the weight of every kind of required material, work out alloy production list of ingredients, and get the raw materials ready by list of ingredients choosing foot is various；
(2) adding appropriate aluminium ingot or molten aluminum liquid in smelting furnace, heating is allowed to melt completely and be incubated more than 700 DEG C；For preventing melt from sucking too much air, fusion process should complete with in enclosed environment the most at short notice；
(3) press formula proportion and add manganese Mn, cadmium Cd, copper Cu, zirconium Zr, after stirring, add selected Lewis Acids and Bases pair, or the Lewis Acids and Bases that addition is selected is to combination, stirs；
If described Lewis Acids and Bases to or combination in solid block, can be directly added into melt or with pressing supplementary mode add melt；
If described Lewis Acids and Bases to or combination in solid filament wire, can be continuously added to when casting, or be cut into suitable segment with on-line automatic wire feeding mode, addition casting ladle or scoop wooden dipper before casting every time；
Described Lewis Acids and Bases pair, active metal element selects to add melt with protection form, and high-melting-point insoluble metal element selects coordination compound form, and readily soluble heavy metal selects elemental stage；
Described Lewis Acids and Bases to or combination, compound or coordination compound select to make pressed powder form in advance；
Described Lewis Acids and Bases to or combination, select to add melt after alloy host element melting completes, or add melt when melt refine, or after refine purifies, add melt, or before cast form, add melt；
(4) then above-mentioned alloy melt carrying out furnace refining, described refine selects to operate in enclosed environment, and described enclosed environment selects to get rid of, in convulsion mode, the waste gas that refine produces continuously；
(5) remove the gred after refine, stand, sample analysis alloy composition, adjust chemical composition in the deviation range of regulation according to analysis result；
Described adjustment selection of chemical composition by add Lewis Acids and Bases to or combination in the way of be adjusted；
Homoiothermic is to more than 650 DEG C, and aluminium alloy is come out of the stove, online degasification, slagging-off；
Described degasification can select the agitation of graphite-pipe sleeve rotor to be blown into purification gas；
Described purification gas can select nitrogen, argon, chlorine or their mixture；
Described slagging-off can select surface remove scum silica frost or select Filtration to remove thick particle in melt or the sediment bottom melt；
Described Filtration can select ceramic filter plate or glass fibre or filter cloth as filter medium；
Described filtration can carry out single-stage filtration or double-stage filtering or multistage filtering；
Described thick particle can be the particle that granularity is not less than 10 microns；
(6) hot top casting: pole casting refers to that aluminium alloy injects continuous crystallisation solidification in crystallizer；
Described crystallizer is casting solid shape metal pattern；
Foundry goods can check presentation quality with naked eyes or by low power magnifier or other test method, and the described visual quality of casting refers to surface roughness, surface defect or dimensional accuracy；Foundry goods is allowed to have the vestiges such as typing, push rod and venting plug, it is allowed to have forging to process eliminable defect, mustn't crackle.
Goods forging molding step:
(1) by upper and lower mould to suitable temperature >=400 DEG C；
(2) heating aluminium bar >=400 DEG C, and put into lower mold；
Described preheating needs special heater, it is desirable to have insulation；
(3) aluminium bar is made to take out cooling after Deformation Flow full mould in mould by pressure；
Described forging needs special mechanized equipment, and forging pressure is more than 4000 tons；
(4) appearance quality detection: size, crackle；
(5) internal soundness detection.Section dye penetrant inspection detection or integral fluorescence or X-ray check；
Described section dye penetrant inspection detects, and can goods random inspection one or the pieces of every batch dissect, and the inspection main heat energy-saving position of goods or wall thickness are compared with the internal soundness of large part；
Described section, can cut the thick large part of the casting position such as housing installation foot, valve body installing hole, side cover installing hole or the master cylinder afterbody etc. that are easily generated most pore, sand holes, detect with coloring agent, estimate whether there is the defect such as pore, sand holes；
Described X-ray check be goods through X-ray transmission to detect its internal metallurgical quality, observe have free of pinholes, pore, shrinkage cavity, loose, shrinkage porosite, segregation, thick phase granule, be mingled with, slag inclusion, cold shut, cold shot or crackle；
(5) solution treatment: forge piece is sent into solid solution furnace, carries out less than 550 DEG C solution treatment, enters water quenching after being incubated at once；
(7) ageing strengthening: the goods completing solution treatment are sent into aging furnace and carries out ageing strengthening process, ageing strengthening below 230 DEG C, natural cooling of coming out of the stove after insulation；
(8) sample analysis test checking: cut coupon from the goods after Overheating Treatment, sampling point is selected in blank body the position that the appropriate location of allowance, body are loaded uniform or concentrate, and each sampling point should cut three coupons；
Sample can be carried out Resarch on A New Type, Metallographic Analysis, secondary densimetry solid solution and timeliness degree detecting or the Micro-Structure Analysis of profound level；
Described mechanics property analysis includes tensile strength, yield strength, elongation percentage, hardness, and numerical indication is: tensile strength 600 ± 50Mpa, yield strength 550 ± 50Mpa, elongation percentage 12 ± 2%, hardness 160 ± 10HBS；
Described Metallographic Analysis includes grain morphology, grain size, thick brittlement phase or notable defect, grain morphology should be equiax crystal, grain size is average≤120 μm, and thick brittlement phase granularity≤25 μm, do not exist more than the notable defect of the hole of 15 μm or precipitate free zone；
The detection solid solution of described secondary densimetry and timeliness degree completion rate are not less than 80%.
(11) Practical Performance checking.Processed and after assembling by machining, surface, be simulated the Practical Performance detection test of applying working condition, including selecting fatigue test, wear test, reverse overload test or overvoltage test.
Part II: specific embodiment
Embodiment 1
1. the aluminium alloy wind power generator blade material weight percentages of components substituting QT600 is: a Mn:0.65%, Cd:0.06%, Cu:7.5%, Si:1.5%, Zr:0.12%, BeH2: 0.02%, W:0.07%, [CoCl4]2-: 0.05%, surplus is aluminum Al；
2, preparation method: melt → hot top casting → pole homogenizing → forging → solid solution → rectification → timeliness
(1) melt temperature >=730 DEG C；
(2) chute preheating temperature >=750 DEG C；
(3) hot top casting temperature >=700 DEG C；
(4) casting speed 80-140 mm/min；
(5) homogenizing temperature >=510 DEG C, are incubated >=1 hour；
(6) upper and lower mold preheating temperature >=400 DEG C are forged and pressed；
(7) aluminium bar heating-up temperature >=400 DEG C；
(8) condition of heat treatment: cold working artificial aging again after T8-solid solution；
3, goods microstructure index: metallographic structure is equiax crystal, mean grain size 60 μm, (T+ θ H) combination phase amount 9/[μm] in crystal grain2；
4, products machinery performance: tensile strength 610Mpa, yield strength 470Mpa, elongation after fracture 10%, Brinell hardness 172.
Embodiment 2
1. the aluminium alloy wind power generator blade material weight percentages of components substituting QT600 is: a Mn:0.8%, Cd:0.08%, Cu:7.8%, Si:1.4%, Zr::
0.18%, BeH2: 0.01%, W:0.08%, [CoCl4]2-: 0.05%, surplus is aluminum Al；
2, preparation method: with embodiment 1；
3, goods microstructure index: metallographic structure is equiax crystal, mean grain size 68 μm, (T+ θ H) combination phase amount 10/[μm] in crystal grain2；
4, products machinery performance: tensile strength 620Mpa, yield strength 480 Mpa, elongation after fracture 12%, Brinell hardness 168.
Embodiment 3
1. the aluminium alloy wind power generator blade material weight percentages of components substituting QT600 is: a Mn:0.8%, Cd:0.08%, Cu:5.4%, Zr:0.18%, BeH2: 0.1%, surplus is aluminum Al；
2, preparation method: with embodiment 1；
3, goods microstructure index: metallographic structure is equiax crystal, mean grain size 68 μm, (T+ θ H) combination phase amount 9/[μm] in crystal grain2；
4, products machinery performance:: tensile strength 610Mpa, yield strength 455Mpa, elongation after fracture 10%, Brinell hardness 170.
Claims (10)
1. the aluminum alloy materials substituting QT600 blade of wind-driven generator, it is characterised in that: main constituent content by weight percentage: manganese Mn :≤2%, cadmium Cd:0.05%～0.5%, copper Cu:4.2%～8.0% and Cu >=0.8Mn+4.05%, zirconium Zr:0.12%～0.20%；Lewis Acids and Bases is to total amount 1% × 10-4～2.0%, making alloy mean grain size ＜ 120 microns, surplus is aluminum Al.
A kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 1, it is characterised in that: alloy grain is equiax crystal.
A kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 1, it is characterised in that: in alloy grain, sub-nanometer (T+ θ H) combination phase amount reaches >=1/square micron.
A kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 1, it is characterised in that: described Lewis Acids and Bases mixes for one or more in metallic hydrogen compound, metal halogen compound, main group dvielement.
A kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 4, it is characterised in that: described metal halogen compound: include four chloro cobalt anion body [CoCl4]2 -。
A kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 4, it is characterised in that: described metal halogen compound, including beryllium hydride BeH2。
7. according to a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator one of claim 1-6 Suo Shu, it is characterized in that: described Lewis Acids and Bases pair, accounting for Al matrix percentage by weight by element addition, scope is: 0.4% ＜ Si ＜ 1.6%, BeH2＜ 0.11%, W ＜ 0.1%, [CoCl4]2 -＜ 0.1%.
The preparation method of a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most as claimed in claim 7, it is characterised in that: comprise the steps of
(1) in the range of aforementioned Lewis Acids and Bases is to, element ratio, selected one group of combinations of substances, determine weight ratio, the alloy total amount prepared as required, extrapolate the weight of every kind of required material；
(2) adding aluminium ingot or molten aluminum liquid in smelting furnace, heating is also incubated more than 700 DEG C；
(3) addition manganese Mn, cadmium Cd, copper Cu, zirconium Zr stir, and add selected Lewis Acids and Bases pair, or the Lewis Acids and Bases that addition is selected is to combination, stirs；
(4) then above-mentioned alloy melt is carried out furnace refining；
(5) remove the gred after refine, stand, sample analysis alloy composition, adjust chemical composition in the deviation range of regulation according to analysis result；Homoiothermic is to more than 650 DEG C, and aluminium alloy is come out of the stove, online degasification, slagging-off；
(6) hot top casting: aluminium alloy is cast as pole；
(7) forging molding: pole forged one-tenth blade blank.
The preparation method of a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 8, it is characterised in that: described hot top casts, and step is as follows:
(1) chute and shunting disk are preheating to suitable temperature；
(2) melt proceeds to shunting disk from holding furnace through chute；
(3) opening cooling water, start casting machine, dummy bar head moves down；
(4) adjusting casting speed 80-140 mm/min, dummy bar head moves down along vertical shaft, and melt flows into crystallizer coagulation forming by chute and shunting disk；
(5) stop casting machine after having cast, close cooling water；
(6) dig shunting disk and hang out aluminium bar, be incorporated to stove homogenizing.
The preparation method of a kind of aluminum alloy materials substituting QT600 blade of wind-driven generator the most according to claim 8, it is characterised in that: described forging molding, step is as follows:
(1) upper and lower mould is preheating to suitable temperature；
(2) heating aluminium bar >=400 DEG C, and put into lower mold；
(3) aluminium bar is made to take out cooling after Deformation Flow full mould in mould by pressure；
(4) appearance quality detection: size, crackle；
(5) solution treatment: forge piece is sent into solid solution furnace, carries out less than 550 DEG C solution treatment, enters water quenching after being incubated at once；
(6) ageing strengthening: the goods completing solution treatment are sent into aging furnace and carries out ageing strengthening process, ageing strengthening below 230 DEG C, natural cooling of coming out of the stove after insulation；
(7) sample analysis test checking；
(8) Practical Performance checking.
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