CN105937000B - A kind of aluminum alloy materials and its centre spinning method substituting QT400 ship columns - Google Patents

A kind of aluminum alloy materials and its centre spinning method substituting QT400 ship columns Download PDF

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Publication number
CN105937000B
CN105937000B CN201610493118.1A CN201610493118A CN105937000B CN 105937000 B CN105937000 B CN 105937000B CN 201610493118 A CN201610493118 A CN 201610493118A CN 105937000 B CN105937000 B CN 105937000B
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alloy
casting
ship
aluminum alloy
columns
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CN105937000A (en
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门三泉
车云
张中可
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Guizhou Huake Aluminium Material Engineering Technology Research Co Ltd
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Guizhou Huake Aluminium Material Engineering Technology Research Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/12Alloys based on aluminium with copper as the next major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00Centrifugal casting; Casting by using centrifugal force
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/057Changing 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 present invention discloses a kind of aluminum alloy materials substituting QT400 ship columns, it is characterised in that:Principal component content is by weight percentage:Lithium:0.4% 0.5%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%, copper Cu:4.2%~8.0% and Cu >=0.8Mn+4.05% or copper 0.5%≤Cu≤3% and Cu >=1.5Mn;For Lewis Acids and Bases to total amount 1% × 10 4~2.0% or 7.0%~9.0%, it is aluminium Al to make 120 microns of alloy mean grain size <, surplus.

Description

A kind of aluminum alloy materials and its centre spinning method substituting QT400 ship columns
Technical field
The present invention relates to a kind of aluminum alloy materials and preparation method thereof substituting QT400 ship columns.
Background technology
Stock number of the aluminium in the earth's crust is considerably beyond iron(Aluminium is 8.2wt%, iron 5.1wt%), and the annual steel production in the whole world 1,200,000,000 tons of sales volume or more, aluminum metal volume of production and marketing only have 0.55 hundred million tons, this huge contrast fully reflect human society to aluminium and The Resources and utilization level of aluminum material lags far behind the development of exploitation level to steel material.
Spheroidal graphite cast-iron(Abbreviation magnesium iron)It is one of the primary base material in steel industry, is heavily used for making extensively Make stress complexity, the more demanding part such as intensity, toughness, wearability, such as universal machine, lifting, agricultural, automobile, casting, spinning It knits, lathe, electric power, petrochemical industry, ship part etc., Main Morphology and type are hydraulic pressure shell, the pump housing, pipeline, valve body, cylinder body, wheel Hub, shaft member, ball connection, driving member, suspender, hook fastener, conducting element, tumbler etc..
Spheroidal graphite cast-iron is widely used, but the manufacture of spheroidal graphite cast-iron production needs to carry out at very high temperatures, phase therewith Corresponding energy consumption is also high, and pollution is big, and with the requirement that lightweight and energy conservation and environmental protection are constantly progressive, related spheroidal graphite cast-iron product is urgent It needs to find new substitute.
In the technology upgrading of " with aluminium for steel ", in order to give full play to aluminium alloy with " light " the superior spy of series for representative Property, it is necessary to so that it is had tremendous development in terms of " strong ", while there cannot be unacceptable manufacturing cost increment, it could significantly It expands it and uses field.This requires must first make a breakthrough in Al-alloy material design.
It is examined closely from the method for material preparation, since material characteristics are combined by carry the microcosmic object of functionality of this feature It contributes, therefore the good functional object of acquisition is combined, such as high intensity, high-melting-point, high-ductility, high rigidity, corrosion resistant Erosion etc. is the final result that various preparation methods are pursued, to, the Design of Chemical Composition of aluminium alloy and its technology of preparing there is Close internal integrity, this uniformity, in short, being the pass how a kind of atom is combined into required " object phase molecule " System, the i.e. object of material mutually can regard a kind of molecular structure as.It is formulated the mixed smelting and casting crystalline of element, is fusion casting shape The major contributing link of material of becoming a useful person phase molecule composite structure, in fusion-casting process, between solid solution crystal grain and the metal of crystal boundary Compound molecule object mutually determines the crystalline state combination (submicron particles of alloy:10~300 μm or so of scale), subsequent heat treatment Or flow harden is then to fine structure (micron particles under crystalline state group frame:1~30 μm or so of scale) or even more Microcosmic precise and tiny structure (Subnano-class or sub-micron grade particle:1 μm of scale 10nm~<) it is adjusted and perfect, this adjustment With perfect degree and range, in known technology and traditional concept, it is believed that mainly by the alloy phase residing for alloy composition The given combined decision of object of graph region, still, alloy phase diagram do not provide the addition of other trace elements and exclude generation It influences, with less the directiveness for prediction addition and excluding other trace elements and mutually being influenced on object.Use for reference alloy solution chemistry Theoretical and method improves melt structure, such as the covering of protective film, the addition of slag former, refining agent or alterant, degasification slagging-off Purification etc., be improve alloy crystalline state combination, fine structure or even more microcosmic precise and tiny structure important technical, but these Means, due to being to grope accumulation during prepare alloy to get, be often considered as " preparation process " rather than " at Set up meter separately " part.
On engineer application, the size and state of aluminum alloy solution body crystal grain, and it is distributed in the intermetallic of crystal boundary The size and form of object has conclusive influence to the mechanical property of alloy.Coarse plane crystalline substance, dendrite, column crystal etc. are no Ordered crystal and the coarse brittle property intermetallic compound for being distributed in crystal boundary, can be the good fine structure of alloy and precise and tiny knot Structure all balances out the obdurability contribution of matrix, because the law of development that these coarse grains are deferred to results from casting mold cavity Type wall gives birth to core, from the unidirectionally extended growth pattern of export-oriented liquid internal, cause the component segregation of alloy, crystallization it is coarse it is unidirectional, The non-uniform defect of macro property, to some common deficiencies as alloy, such as pin hole, stomata, shrinkage cavity and porosity, segregation, thick The root of big solid solution, high hardness compound, crackle etc..The means of the routine rotten means and crystal grain thinning that use at present, such as Add aluminium titanium boron or Al-Ti-C master alloy, best effect can only make mean grain size refine to 120~150 microns, and branch The often not basic transformation of brilliant form, this is the important bottleneck problem that alloy mechanical property improves.Because being closed to aluminium For gold, the approach that intensity and toughness improve simultaneously, the only refinement of crystal grain and rounding are obtained;The adjustment of heat treatment process, In the state that crystalline structure has determined, intensity or toughness can only be made to be optimized on one side.Therefore, how further thin Change the mean grain size with rounding alloy, is the target that industrial circle is pursued always.
In terms of material design angle, 211Z materials are difficult to overcome the problems, such as there is also some.Micro-analysis is found, is had Bulky grain has very high titanium Ti and rare earth concentration, as promoting the substance of crystal grain refinement, this phenomenon to show Ti and rare earth The opposite for needing to solve the problems, such as is moved towards;And in the production process of 211Z alloy-steel castings, also occur and common aluminum alloy Equally common defect, including pin hole, stomata, shrinkage cavity and porosity, segregation, coarse solid solution, high hardness compound, be mingled with (slag), Cold shut, cold shot, crackle, rotten defect, solid solution deficiency and burning etc..
These defects, main cause still will start with from the chemical composition of alloy itself and its microcosmic phase structure of formation It studies, especially the formation mechenism of object phase molecule composite structure is furtherd investigate, can just see clearly essence, and then finds solution Certainly problem, the effective way of elimination defect.
It is saturating by the spherical aberration correction scanning for being up to the very high resolution of 0.08nm to aluminum bronze manganese systems (Al-Cu-Mn) alloy The precise and tiny constituency analysis of electron microscope (STEM) is penetrated, various phase structures, the Atomic Resolution established on an atomic scale are obtained It is distributed with chemical element.Confirm wherein there are a series of hardening constituents, including well-known Al-Cu binary metastable phase (areas GP, θ ", θ '), new disc phase and balance phase θ (Al2Cu);Wherein inside matrix grain, a kind of forked (the T+ θ H) group of stick of new discovery Phase is closed, the trunk portion T-phase of the combination phase is Al-Cu-Mn ternary phases, molecular structural formula Al20Cu2Mn3, molecule phase character is Diameter about 100nm, length about 600~1000nm are in mandrel shape and { 010 } face coherence in its (010) face and alloy matrix aluminum;And T The apposition growth secondary phase of Al-Cu binary of size larger (thickness about 20nm, being about 50nm) around phase, due to the secondary phase with Other Al-Cu metastable phases (areas GP, θ ", θ ' or other disc phases) are compared in matrix, have very big difference in structure, especially Thickness is much thicker than other Al-Cu metastable phases, therefore the present invention is referred to as θ H phases, molecular structural formula Alx(x is likely less than Cu 2), it is a kind of richness Cu molecules.
According to alloy strengthening theory, the intensity of alloy is that material median surface or dislocation movement by slip are generated by the obstruction of particle , obstruction is stronger, and the intensity of material is also bigger.And particle hinders the knot that behavior interacts with material median surface or dislocation movement by slip Fruit, there are two types of:One is when particle strong hardness itself is not high enough, dislocation will cut through particle and continue to slide, and another kind is particle Intensity is very high, and dislocation can not be cut through, then can only continue to slide around particle, and a circle dislocation ring is left around particle.
The size that two kinds of results contribute the strength of materials is obvious:Particle is cut through to the strength of materials around particle ratio Contribution it is big;It cuts through particle and is capable of providing the preferable elongation percentage of material, and will be carried due to the humidification of dislocation ring around particle For the higher yield strength of material and tensile strength.
Aluminium boat column has correlative study at home, but because of the limitation of basic material, mechanical property is relatively low, especially It is tensile strength and poor corrosion resistance, has seriously affected the service life of ship column, increases the use cost using department and maintenance Cost, or even increase security risk.
Invention content
The technical problem to be solved by the present invention is to:There is provided it is a kind of substitute QT400 ship columns aluminum alloy materials and its preparation side Method, wherein addition Lewis Acids and Bases pair, effectively to expedite the emergence of critical nucleus(Obtain equiax crystal), alloy is made to obtain before curing most The good combined structure of molecule object((T+ θ H) combines phase), promote alloy crystalline state optimize, enable aluminum alloy to base material realize 400MPa and Higher strength grade, to reach the Al-alloy products that production substitutes QT400 ship columns.
The technical scheme is that:A kind of aluminum alloy materials substituting QT400 ship columns, principal component content percentage by weight Than meter:Lithium Li:0.4%-0.5%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%, copper Cu:4.2%~8.0% and Cu >=0.8Mn+ 4.05% or copper 0.5%≤Cu≤3% and Cu >=1.5Mn;Lewis Acids and Bases to total amount 1% × 10-4~2.0% or 7.0%~9.0%, It is aluminium Al to make 120 microns of alloy mean grain size <, surplus.
The alloy grain is equiax crystal.
Sub-nanometer (T+ θ H) combination phase amount reaches >=1/square micron in the alloy grain.
The Lewis Acids and Bases are to for positive and negative ion body made of metal and ligand binding, complicated ligand compound, super large Heteropoly compound, the nitride of metal, one kind in transition group dvielement or more than one mixing.
Cation body, anion body made of the metal and ligand binding include that chlordene closes chromium anion body [CrCl6]3-
The complicated ligand compound or super large heteropoly compound includes phosphotungstic acid H3[P(W3O10)4]。
The Lewis Acids and Bases pair account for Al matrix weight percent, ranging from by element additive amount:Zr < 0.3%, W < 0.5%, Y < 0.15%, [CrCl6]3-< 0.5%, WN2< 0.05%, H3[P(W3O10)4] < 0.05%.
A kind of preparation method for the aluminum alloy materials substituting QT400 ship columns, comprises the steps of:
(1) weight ratio is determined within the scope of, element ratio, selecting one group of substance combination in aforementioned Lewis Acids and Bases, according to The alloy total amount prepared is needed, the weight of each required material is extrapolated;
(2) aluminium ingot or molten aluminum liquid are added into smelting furnace, heat and is kept the temperature at 700 DEG C or more;
(3) manganese Mn, cadmium Cd, copper Cu is added, selected Lewis Acids and Bases pair are added in lithium Li stirrings, or are added selected Lewis Acids and Bases stir evenly combination;
(4) and then to above-mentioned alloy melt furnace refining is carried out;
(5) slagging-off, standing, sampling analysis alloy composition after refining adjust chemical composition according to analysis result and extremely advise In fixed deviation range;To 650 DEG C or more, aluminium alloy is come out of the stove for temperature adjustment, online degasification, slagging-off;
(6) it casts:It is poured into a mould using centrifugal casting.
The centrifugal casting cast, steps are as follows:
1. pourable casting after filtering;
2. should preheat mold before casting, sand core is installed, is blown clean mold cavity with compressed air;
3. starting centrifugal device, artificial cast or automation cast are taken, aluminium alloy is dipped out of stove with casting ladle and pours into mould Have cast gate and cavity is full of by ingate;Natural cooling is strong cold;
4. product, natural cooling, cleaning sand core, sawing riser, polishing overlap are taken out in die sinking;
5. appearance quality detection:Rough casting should clean out smooth, non-processing face before carrying out presentation quality inspection Dead head should be cleaned to cast(ing) surface and flush;
6. internal soundness detects;
7. solution treatment:The blank that casting is completed to roughing and inside and outside quality testing is sent into solid solution furnace, carry out 560 DEG C with Lower solution treatment quenches after the completion of heat preservation, uses water cooling or oil cooling at once;
8. ageing strengthening:The casting for completing solution treatment is sent into aging furnace and carries out ageing strengthening processing, at 230 DEG C or less Ageing strengthening, after heat preservation, natural cooling of coming out of the stove;
9. sampling analysis test verification;
10. practical performance is verified.
Beneficial effects of the present invention:It is pointed by lewis' theory of acids and bases, molecule solution can occur in aluminium alloy melt Body or " acid-base pair " substance for contributing in time nano-area (range for being less than 1 nanometer) object phase molecule structure optimization, application It is adjusted in the fine structure of melt nanoscale range, is the most important creative technological means of the present invention.
By using lewis' theory of acids and bases, make addition and exclusion to the trace element of carrying in relation to Lewis Acids and Bases, Molecule disintegration and conversion occurs in aluminium alloy melt environment, to provide in the hyperfine microcell of melt (0.1nm~10nm scale models Enclose) abundant disturbance and activation effect, reach and expedite the emergence of critical nucleus and largely formed, alloy grain degree is made further to be refined, Form more rounding;Optimize very small areas (micron order simultaneously:1~30 μm or so of scale) and (Subnano-class is secondary in precise and tiny region Micron order particle:1 μm of scale 10nm~<) object phase molecule composite structure, increase (T+ θ H) combination mutually in alloy substrate Content is the mechanism problem for the alloy strengthening that the present invention solves.
The aforementioned Lewis Acids and Bases of the present invention are to for positive and negative ion body made of metal and ligand binding, complicated ligand chemical combination Object, super large heteropoly compound, the nitride of metal, one kind in transition group dvielement or more than one mixing.
For example, anion body [CrCl6]3-It is Louis's " acid-base pair ", the Cr that can receive electronics pair in substance+It is road Lewis acid, the corresponding ligand-Cl for providing electronics pair is lewis base.
Cation body and anion body have ordinary matter can not be real alloy grain refinement as Louis " acid-base pair " Existing excellent effect, this is because:These gas ions can be stabilized as normal material molecule at normal temperatures, and in aluminium Molecule occurs in high temperature acid or alkali environment as alloy melt to disintegrate, generates lewis acid and lewis base;Due to being molecule solution Body, so being a kind of " the falling apart " of the atom composite structure of secondary nanometer range, ligand moiety is come out with gaseous exhaust, is released The core metal ion come is then reselected in conjunction with other atoms.
This disintegration and reconstruct being happened in aluminium alloy melt, it is different from common substance dissolving, because:1. under high temperature Decomposing the incipient bubble that the gaseous material discharged is formed, only there are one molecular size (being less than 1nm, i.e. secondary nanophase), specific surface areas Maximum has the disturbance ability of extremely strong activity and nanometer range, is in the size range that crystallization critical nucleus is formed, thus The states such as fluctuation of energy, rise and fall of structure and composition fluctuations of atom rise and fall all with extremely strong in melt superfinishing microcell caused by and Characteristics of Mutation promotes neighbouring more polyatom across crystallization potential barrier, so a large amount of formation of critical nucleus are particularly conducive to, to gold The catalysis of compound reaction of formation and alloy structure crystal grain refinement all produce good better than common alterant such as aluminium titanium boron between category Effect;Positive and negative ion body this disturbance and activation effect in the superfinishing microcell of secondary nanometer range simultaneously is conventional additional purification What the bubble (diameter is more than 0.5mm) that gas is formed cannot achieve;2. the metallic atom or cation that decompose release have than matching The specific surface area of body smaller volume and bigger, it is stronger to the disturbance and activation effect of neighboring atom, caused by superfinishing microcell State fluctuating is more notable, also stronger to intermetallic compound reaction of formation catalysis and alloy substrate tissue Grain Refinement Effect; It, will not be as common gold 3. division and reconstruct of the acid-base pair in high-temperature fusant enhance dispersion and diffusion velocity of the particle in microcell Belong to or additive causes clustering like that, and restrained effectively caused by additive alloying component segregation and bulky grain matter Point aggregation and grow up, this can effectively solve conventional grain fining agent coarsening tendency in crystallization process, such as can prevent The roughening of titanium Ti and rare-earth phase;4. secondary reaction can also occur for ligand bubble, purification gas is accompanied after a series of variations Discharge melt (for example generate CO2、CH4、N2、NH3Or H2S) or enter slag (such as Al2O3、Al(HO)3Or Al4C3), it is this net Change acts on, can be with most stable of solid-state or gaseous material, and the H dissolved in the melt and oxide impurity absorbs and decomposition, To which its catharsis is more preferable than conventional gas purification mode effect.Here it is positive and negative ion bodies as Lewis Acids and Bases pair Addition and exclusion, aluminium alloy melt environment occur molecule disintegrate, atom reconstruct in acid-base chemical conversion and superfinishing microcell, to provide Abundant disturbance in melt superfinishing microcell and activation effect reach and expedite the emergence of critical nucleus largely generation and the inhibition long your writing of crystal grain With, and realize the mechanism of more preferable clean-up effect.By this mechanism, matrix crystalline state is made generally to become equiax crystal, grain size Averagely it is less than 120 μm, it is average at 50~100 μm that further effect of optimization can reach grain size.This effect is to use merely What the conventional grains such as aluminium titanium boron and aluminium titanium carbon fining agent and the gas purification technique of routine cannot achieve.
Complicated ligand compound, super large heteropoly compound also have alloy grain refinement general as Lewis Acids and Bases pair The good result that logical substance cannot achieve can close because their molecular structure is similar with the structure of positive and negative ion body in aluminium Atom reconstruct in disintegration, acid-base chemical conversion and the superfinishing microcell of molecule occurs in environment as golden melt, can also disintegrate in molecule When release gaseous state or the ligand of liquid, purification gas discharge melt is accompanied after series reaction and (for example generates CO2、CH4、 N2、NH3Or H2S) or enter slag (such as NaCl, KCl, Al (HO)3、Al2O3Or Al4C3), wherein the metallic atom that discharges or from Son, non-metallic atom or ion are all the ultra-fine fine particles of secondary nanophase, there is maximum specific surface area, and it is super to provide melt Abundant disturbance in precise and tiny area and activation effect reach and expedite the emergence of critical nucleus and largely generate and crystal grain is inhibited to grow up the machine of effect Reason.By this mechanism, matrix crystalline state is made generally to become equiax crystal, grain size is averagely less than 120 μm, further optimization It is average at 50~100 μm that effect can reach grain size.This effect is thin using the conventional grains such as aluminium titanium boron and aluminium titanium carbon merely What the gas purification technique of agent and routine cannot achieve.
When the external Lewis Acids and Bases being added in melt are to decomposing, the intermetallic compound with matrix Presence of an interface energy difference Presoma is obviously also disturbed and activates and recurring structure rises and falls, and generates more critical nucleus, and (T+ θ H) combination is made mutually to exist Concentration in alloy and be evenly distributed density, make up to 1/[μm]2More than, here it is Lewis Acids and Bases in nanoscale Disturbance and activation effect can increase Subnano-class particle (T+ θ H) combination mutually and the areas nanoscale particle GP, θ ", θ ' series are strong Change the mechanism of phase.
To sum up, Lewis Acids and Bases pair of the present invention can show as variform, including metal is formed with ligand binding Positive and negative ion body, complicated ligand compound, super large heteropoly compound, the nitride of metal, one in transition group dvielement Kind or more than one mixing.
In addition, since Lewis Acids and Bases are to being capable of providing to foreign peoples's material concentration of alloy melt bigger, increase The constitutional supercooling degree of melt crystallization process causes nucleus quickly to cross critical dimension under stronger crystallization power, and in supercooling It is freely nucleated and grows in liquid, being formed has isotropism and shape closer to spherical equi-axed crystal;Therefore avoid or Component segregation, coarse unidirectional, the non-uniform defect of macro property of crystallization for alleviating alloy, to effectively avoid or alleviate conjunction Some common deficiencies of gold, such as pin hole, stomata, shrinkage cavity and porosity, segregation, coarse solid solution, high hardness compound, crackle.
The present invention is based on to alloy microstructure very high resolution contrast image and precise and tiny constituency structural analysis, it was found that It is transgranular that there is the hyperfine structures of the forked combination phase of (T+ θ H) stick of sub-micron grade.Compared with each binary of Al-Cu, (T+ θ H) Combination mutually has many advantages, including:Particle size is big, and anti-dislocation movement by slip face is big;Trunk portion T is that high hard high stable compound is poly- Rodlike twin made of conjunction can provide strength support around mode using dislocation as alloy;Its secondary θ H attachment is mutually on trunk It is oblique or perpendicular to T mandrels direction and to surrounding matrix grow simultaneously with matrix coherence, enhance trunk to lattice-site around The tightening ability of battle array, or, in other words, T mandrels by adhering to thereon to the secondary phases of θ H of surrounding growth, tightening act on to The matrix space of surrounding is transmitted and diffusion, this effect, and steel in similar building structure is produced to matrix in secondary um region Invigoration effect (can be described as " class concrete reinforced structure ") of the reinforced net in concrete, makes matrix strength greatly improve.This effect, It is flake Al-Cu metastable phases in matrix (areas GP, θ ", θ ' or other disc phases) if compared from monomer All far from compared to;But in common aluminum bronze manganese systems (Al-Cu-Mn) alloy, since each binary Al-Cu metastable phases exist The distribution density of intrinsic silicon is significantly larger than the distribution density of (T+ θ H) combination phase, and the effect of (T+ θ H) combination phase is caused to be blanked And it is never found.
(T+ θ H) combine phase in θ H but with different positions to much bigger thickness (about 20nm), alloy substrate is produced Better than the reinforcing contribution with the binary Al-Cu metastable phases in the areas GP, θ ", θ ' or other disc shapeds existing for free state:θ H in addition to The tightening of trunk T-phase is acted on peripherad matrix space transmission and diffusion is outer, due to anti-matrix slide surface bigger, therefore to matrix Humidification bigger;Since direction is more, therefore isotropic uniformity is showed to the invigoration effect of matrix;Due to being not belonging to height Rigid particle, so can still be supplied to the preferable plasticity and toughness of matrix in such a way that dislocation is cut through;In short, (T+ θ H) combination mutually optimizes The object phase molecule composite structure of aluminum bronze manganese systems (Al-Cu-Mn) alloy provides being imitated around reinforcing for high Hard Inclusion T-phase for matrix It should be acted on higher than metastable combined two kinds of the strengthening effects that cut through of free state Al-Cu;So research play it is this excellent comprehensive Close effect, it is necessary to the emphasis of design of material concern from tradition merely it is metastable to Al-Cu it is combined be transferred out, and concentrate on pair (T+ θ H) combination phase expedites the emergence of in effect.
Inventive formulation is configured as one of technical way, is to make the crystalline state of alloy combine to realize mean grain size < Under the premise of 120 microns of equiax crystal, can also be achieved inside alloy grain (T+ θ H) combination phase amount 1/[μm]2More than.Cause This, principal component content is by weight percentage:Lithium Li:0.4%-0.5%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%, copper Cu: 4.2%~8.0% and Cu >=0.8Mn+4.05% or copper 0.5%≤Cu≤3% and Cu >=1.5Mn;Lewis Acids and Bases to total amount 1% × 10-4~2.0% or 7.0%~9.0%, it is aluminium Al to make 120 microns of alloy mean grain size <, surplus.By adding lithium Li in alloy Middle formation Al2Li3、AlLi5Deng 5 kinds of dispersivity High-Temperature Strengthening phases, the hardness and corrosion resisting property of alloy can be improved, is mechanical index Provide material base.
Specific implementation mode
The specific embodiment of the invention includes 2 parts, and first part is prompt and explanation, and second part is specific implementation Example.
First part:Prompt and explanation
The centrifugal casting, steps are as follows:
1, using metal type dies, preheating is more than 350 DEG C;
2, aluminium ingot or molten aluminum liquid are added into smelting furnace for melting, heat and are kept the temperature at 700 DEG C or more;
3, alloying, is added manganese Mn, cadmium Cd, copper Cu, and selected Lewis Acids and Bases pair are added, or are added in lithium Li stirrings Selected Lewis Acids and Bases stir evenly combination;
4 and then above-mentioned alloy melt refined with refining agent in stove;
5, slagging-off, standing, sampling analysis alloy composition after refining adjust chemical composition according to analysis result and extremely provide Deviation range in;To 660 DEG C or more, aluminium alloy is come out of the stove for temperature adjustment, online degasification, slagging-off;
6, artificial cast or automation cast are taken after filtering, aluminium alloy is dipped out of stove with casting ladle, and to pour into mould gate logical Ingate is crossed full of cavity and starts centrifugal casting;Natural cooling is strong cold;
7, product, natural cooling, cleaning surface molding sand, sawing riser, polishing overlap are taken out in die sinking;
8, appearance quality detection:Rough casting should clean out smooth, non-processing face before carrying out presentation quality inspection Dead head should be cleaned to cast(ing) surface and flush;
9, internal soundness detects;
10, solution treatment:The blank that casting is completed to roughing and inside and outside quality testing is sent into solid solution furnace, carries out 560 DEG C Following solution treatment quenches after the completion of heat preservation, uses water cooling or oil cooling at once;
11, ageing strengthening:Will complete solution treatment casting be sent into aging furnace carry out ageing strengthening processing, 230 DEG C with Lower ageing strengthening, after heat preservation, natural cooling of coming out of the stove.
Second part:Specific embodiment
Embodiment 1
1, a kind of aluminum alloy materials composition by weight percent substituting QT400 ship columns is:Lithium Li:0.5%, copper Cu:5.4%, Manganese Mn:0.6%, cadmium Cd:0.15%, zirconium Zr:0.2%, tungsten W:0.43%, yttrium Y:0.14%, chlordene closes chromium anion body [CrCl6]3-: 0.05%, tungsten nitride WN2:0.05%, phosphotungstic acid H3[P(W3O10)4]:0.05%;
2, preparation method:Melt → cast → rotation cavity → mold filling and solidification → stalling molds pickup → solid solution → timeliness;
3,660 DEG C of melt cast temperature >;
4,350 DEG C of mold preheating temperature >;
5, filling time < 30s;
6,2 min of cavity rotating speed > 500r/min, retention time >;
7, it is heat-treated:T6-solid solution adds full artificial aging;
8, cast microstructure index:Metallographic structure is equiax crystal, 80 ~ 100 μm of mean grain size, (T+ θ H) group in crystal grain Close phase amount 2 ~ 4/[μm]2
9, casting mechanical performance
Power resistance strength Mpa Yield strength Mpa Hardness HB Elongation after fracture %
480 490 140 7.8
Embodiment 2
1, a kind of aluminum alloy materials composition by weight percent substituting QT400 ship columns is:Lithium Li:0.4%, copper Cu:5.5%, Manganese Mn:0.8%, cadmium Cd:0.1%, zirconium Zr:0.2%, tungsten W:0.4%, yttrium Y:0.1%, chlordene closes chromium anion body [CrCl6]3-: 0.05%, tungsten nitride WN2:0.05%, phosphotungstic acid H3[P(W3O10)4]:0.05%;
2, specific preparation method is same as Example 1;
3, product microstructure index:Metallographic structure is equiax crystal, 80~120 μm of mean grain size, in crystal grain (T+ θ H) Combine phase amount 2~3/[μm]2
4, casting mechanical performance
Power resistance strength Mpa Yield strength Mpa Hardness HB Elongation after fracture %
460 475 135 7.8
Embodiment 3
1, a kind of aluminum alloy materials composition by weight percent substituting QT400 ship columns is:Lithium Li:0.45%, copper Cu:2.5%, Manganese Mn:0.8%, cadmium Cd:0.1%, phosphotungstic acid H3[P(W3O10)4]:0.05%;
2, specific preparation method is same as Example 1;
3, product microstructure index:Metallographic structure is equiax crystal, 80~120 μm of mean grain size, in crystal grain (T+ θ H) Combine phase amount 2~3/[μm]2
4, casting mechanical performance
Power resistance strength Mpa Yield strength Mpa Hardness HB Elongation after fracture %
465 480 139 7.1

Claims (5)

1. a kind of aluminum alloy materials substituting QT400 ship columns, it is characterised in that:Principal component content is by weight percentage:Lithium Li: 0.4%-0.5%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%, copper Cu:4.2%~8.0% and Cu >=0.8Mn+4.05% or copper 0.5% ≤ Cu≤3% and Cu >=1.5Mn;Surplus is aluminium Al;Additive total amount 1% × 10-4~2.0% or 7.0%~9.0%, so that alloy is averaged 120 microns of grain size <, sub-nanometer (T+ θ H) combination phase amount reaches >=1/square micron in alloy grain;In alloy grain The molecular structural formula that sub-nanometer (T+ θ H) combines phase is (Al20Cu2Mn3+AlxCu);Wherein x be less than 2, θ H phases thickness be 20nm, A length of 50nm;The additive is phosphotungstic acid H3[P(W3O10)4], chlordene closes chromium anion body made of metal and ligand binding [CrCl6]3-、WN2In one or more kinds of mixing or transition group dvielement in a kind of one kind with aforesaid compound The above mixing.
2. a kind of aluminum alloy materials substituting QT400 ship columns according to claim 1, it is characterised in that:Alloy grain is Equiax crystal.
3. a kind of aluminum alloy materials of replacement QT400 ship columns according to one of claim 1-2, it is characterised in that:It is described Additive accounts for Al matrix weight percent, ranging from by element additive amount:Zr < 0.3%, W < 0.5%, Y < 0.15%, [CrCl6]3-< 0.5%, WN2< 0.05%, H3[P(W3O10)4] < 0.05%.
4. a kind of preparation method of aluminum alloy materials substituting QT400 ship columns as claimed in claim 3, it is characterised in that:Packet Containing following steps:
(1) within the scope of aforementioned additive, element ratio, one group of substance combination is selected, weight ratio is determined, prepares as needed Alloy total amount extrapolates the weight of each required material;
(2) aluminium ingot or molten aluminum liquid are added into smelting furnace, heat and is kept the temperature at 700 DEG C or more;
(3) manganese Mn, cadmium Cd, copper Cu is added, selected additive is added in lithium Li stirrings, or selected additive combination is added, It stirs evenly;
(4) and then to above-mentioned alloy melt furnace refining is carried out;
(5) slagging-off after refining is stood, sampling analysis alloy composition, and chemical composition is adjusted to defined according to analysis result In deviation range;To 650 DEG C or more, aluminium alloy is come out of the stove for temperature adjustment, online degasification, slagging-off;
(6) it casts:It is poured into a mould using centrifugal casting.
5. a kind of preparation method of aluminum alloy materials substituting QT400 ship columns according to claim 4, it is characterised in that institute Centrifugal casting cast is stated, steps are as follows:
1. pourable casting after filtering;
2. should preheat mold before casting, sand core is installed, is blown clean mold cavity with compressed air;
3. starting centrifugal device, artificial cast or automation cast are taken, out of stove aluminium alloy is dipped with casting ladle and pours into mold and pour Mouth is full of cavity by ingate;Natural cooling is strong cold;
4. product, natural cooling, cleaning sand core, sawing riser, polishing overlap are taken out in die sinking;
5. appearance quality detection:Rough casting should be cleaned out smooth before carrying out presentation quality inspection, and non-processing face is poured Riser should be cleaned to cast(ing) surface and flush;
6. internal soundness detects;
7. solution treatment:The blank that casting is completed to roughing and inside and outside quality testing is sent into solid solution furnace, carries out 560 DEG C or less admittedly Molten processing quenches after the completion of heat preservation, uses water cooling or oil cooling at once;
8. ageing strengthening:The casting for completing solution treatment is sent into aging furnace and carries out ageing strengthening processing, in 230 DEG C or less timeliness Strengthen, after heat preservation, natural cooling of coming out of the stove;
9. sampling analysis test verification;
10. practical performance is verified.
CN201610493118.1A 2016-06-29 2016-06-29 A kind of aluminum alloy materials and its centre spinning method substituting QT400 ship columns Expired - Fee Related CN105937000B (en)

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