CN105936991B - A kind of aluminum alloy materials and squeeze cast form method substituting QT500 automobile connecting bars - Google Patents
A kind of aluminum alloy materials and squeeze cast form method substituting QT500 automobile connecting bars Download PDFInfo
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- CN105936991B CN105936991B CN201610492978.3A CN201610492978A CN105936991B CN 105936991 B CN105936991 B CN 105936991B CN 201610492978 A CN201610492978 A CN 201610492978A CN 105936991 B CN105936991 B CN 105936991B
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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
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D18/00—Pressure casting; Vacuum casting
- B22D18/02—Pressure casting making use of mechanical pressure devices, e.g. cast-forging
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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
- 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
- C22F1/043—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 silicon as the next major constituent
Abstract
The present invention discloses a kind of aluminum alloy materials substituting QT500 automobile connecting bars, it is characterised in that：Principal component content is by weight percentage：Five cyanogen close nickel anion body [Ni (CN) 5] 3：0.05% 0.15%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%, copper Cu0.5~3% and Cu >=1.5Mn；Lewis Acids and Bases are aluminium Al to total amount 7.0%~9.0%, 120 microns of alloy mean grain size ＜, surplus.
Description
Technical field
The present invention relates to a kind of aluminum alloy materials and preparation method thereof substituting QT500 automobile connecting bars.
Background technology
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.；In the automotive industry, the use of steel material
Amount accounts for the 60~70% of Vehicle Materials total amount, and therein 2/3rds or more be magnesium iron class ferroalloy again.
Why widely used magnesium iron is, and also residing in it has the standard brand of subdivision, each trade mark defines more stringent
Accurate chemical composition combination, specification of heat treatment parameter, mechanical property and physical index etc., to correspond to subdivision application products
Class.
Pursue low-carbon, intensive, high efficiency（It is high-effect）, flexibility and personalization, be manufacturing industry from traditional form to height
The mark for holding form to cross over generally substitutes steel weight strong structure with aluminium for steel, with light strong structure, is the main of this leap of realization
Means.
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.
The tough cast aluminium alloy gold of 211Z heat-resistance high-strengths is because having " four high three is good " feature（I.e. high-strength, high-ductility, high hard, high temperature resistant,
While good casting property, processing performance are good, good cycle）And enter the aluminum material leading level in the world.
But in terms of material design angle, 211Z materials are difficult to overcome the problems, such as there is also some.Micro-analysis discovery,
There are some bulky grains to have very high titanium Ti and rare earth concentration, as promoting the substance of crystal grain refinement, this phenomenon to show Ti
The opposite for needing to solve the problems, such as has been moved towards with rare earth；And in the production process of 211Z alloy-steel castings, also occur with it is common
The equally common defect of aluminium alloy, including pin hole, stomata, shrinkage cavity and porosity, segregation, coarse solid solution, high hardness compound, folder
Miscellaneous (slag), cold shut, cold shot, crackle, rotten defect, solid solution is insufficient and burning etc..
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.
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.
In the traditional concept about aluminum bronze manganese systems (Al-Cu-Mn) alloy, due to always all thinking that Al-Cu Binary-phases are
The principal element of alloy strengthening, therefore, the emphasis of investigation of materials and design concern exactly makes each metastable state of Al-Cu Binary-phases real
Now optimal combination in the alloy.Although it has also been found that there is T ternary phases, being not to be considered as T-phase can be with to the contribution of alloy strength
The combination of each metastable phase of Al-Cu binary is compared, and thinks that T-phase is easy to assemble to form coarse brittlement phase in crystal boundary, therefore tight
Lattice control its quantity.
The areas GP, θ ＂, θ ＇ or other disc shapeds the contribution feature of the metastable golden intensity that is involutory of binary Al-Cu belong to dislocation
Particle mode is cut through, its main feature is that disc grows bigger, cuts through more difficult therefore also bigger to the contribution of intensity, still, works as disk
Piece greatly to a certain extent (diameter is more than 150nm and thickness only has 1~3nm), the mismatch of lattice dot matrix and matrix lattice dot matrix
Height is spent, just no longer can keep complete coherence with matrix, and gradually shows the feature of brittlement phase.Therefore, coherence should be kept again
There is maximum mismatch stress field to play maximum obstruction dislocation movement by slip ability, there are one best for each metastable phase particles of binary Al-Cu
The problem of combination, while being also required to it and larger contribution is kept to the elongation percentage of matrix, before this is or even from now on design of material
Always one of main problem to be considered.
Currently, domestic aluminum alloy connecting rod is all made of 1 serial cast aluminium alloy gold manufacture, alloy maximum intensity 450Mpa with
Under, material property does not catch up with the demand of automotive engineering, limits the popularization of aluminium alloy automobile connecting rod.
Invention content
The technical problem to be solved by the present invention is to：A kind of aluminum alloy materials and its system substituting QT500 automobile connecting bars are provided
Preparation 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
Obtain the combined structure of molecule object most preferably（(T+ θ H) combines phase）, promote alloy crystalline state to optimize, enable aluminum alloy to base material realization
500MPa and higher strength grade, to reach the Al-alloy products that production substitutes QT500 automobile connecting bars.
The technical scheme is that：A kind of aluminum alloy materials substituting QT500 automobile connecting bars, principal component content is by weight
Percentages：Five cyanogen close nickel anion body [Ni (CN)5]3-：0.05%-0.15%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%,
Copper Cu0.5~3% and Cu >=1.5Mn；For Lewis Acids and Bases to total amount 7.0%~9.0%, 120 microns of alloy mean grain size ＜ is remaining
Amount is aluminium Al.
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 to for metal and cation body made of ligand binding, complicated ligand compound or super large it is miscellaneous
Owner same clan element, one kind in transition group dvielement or more than one mixing are closed in polyvoltine.
Cation body made of the metal and ligand binding：Iron cation body [Fe is closed including different sulphur cyanogen（NCS）]2+。
The complicated ligand compound or super large heteropoly compound, including [Ag (NH3)2]Cl。
The Lewis Acids and Bases pair account for Al matrix weight percent, ranging from by element additive amount：Li≤0.3%,
Si7.5-9.0%, Mg0.3-0.45%, Ti0.1-0.2%, [Ag (NH3)2]Cl ≤0.03%。
A kind of preparation method for the aluminum alloy materials substituting QT500 automobile connecting bars, 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 and five cyanogen are added and close nickel anion body [Ni (CN)5 ]3-, stir, selected Louis be added
This acid-base pair, or selected Lewis Acids and Bases are added to combination, it stirs evenly；
(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) extrusion casint：Refer to pressurizeing in molten condition in aluminium alloy injection running gate system and filling type, solidification and crystallization.
The extrusion casint, steps are as follows：
1. pouring into a mould casting after filtering；
2. should preheat mold before casting, sand core is installed, is blown clean mold cavity with compressed air；
3. taking automatic casting, aluminium alloy is dipped out of stove and pours into ingot-containing tube, ingot-containing tube is moved to mould gate, melt
Extrusion forming when state, pressurize solidification and crystallization.
4. product, natural cooling, 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.
Since (T+ θ H) combines the discovery of phase, in aluminium alloy strengthening design, so that it may to combine phase by increase (T+ θ H),
The matrix strength for enabling aluminum alloy to material obtains big promotion, is well controlled between 400~600MPa in yield strength, this
Be the invention solves engineer application problem, i.e. alternate series ductile iron material and product.
According to lewis' theory of acids and bases, acid is can arbitrarily to connect nucleophobic molecule or ion, and alkali is can to provide electronics
Molecule or ion, the chemical combination between soda acid is combined with covalent bond, and electronics transfer does not occur.
All metals and it is nonmetallic between the complex that generates, can regard as " acid-base pair ".It is managed according to Lewis Acids and Bases
By when metal and ligand are close, energy level splitting will be occurred, formed between metal and ligand and thermal chemical reaction occurs and is formed opposite
Stable complex.
Aforementioned metal of the present invention and negative ions body, complexity ligand compound or the miscellaneous polyvoltine of super large made of ligand binding
Close object, due in its lewis' acid structure metallic atom or ion be electron acceptor, be lewis acid, and the non-gold of its ligand
It is electronq donor to belong to atom or atomic group, is lewis base, and entire lewis' acid then constitutes Louis's " acid-base pair ".
Cation body has the excellent effect that ordinary matter cannot achieve as Louis " acid-base pair ", to alloy grain refinement
Fruit, this is because：These gas ions can be stabilized as normal material molecule at normal temperatures, and aluminium alloy melt this
Molecule occurs in the high temperature acid or alkali environment of sample to disintegrate, generates lewis acid and lewis base；Due to being molecule disintegration, so be one
" falling apart " of the atom composite structure of kind time nanometer range, ligand moiety is come out with gaseous exhaust, the core gold released
Belong to ion then to reselect in conjunction with other atoms.
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 be in aluminium alloy because their molecular structure is similar with the structure of cation body
Atom reconstruct in disintegration, acid-base chemical conversion and the superfinishing microcell of molecule occurs in environment as melt, it also can be when molecule disintegrates
Gaseous state or the ligand of liquid are released, 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.
In alloy melt, different metal atom or ion it is close, also will produce energy level splitting between them and heat occur
Chemical reaction (electronics transfer does not occur) and form the pattern of intermetallic compound, point of matrix crystalline state is different from due to foring
Minor structure has preferable thermal stability, so it is also suitable lewis' theory of acids and bases.Such as in intermetallic compound molecule
AlxCu and Al20Cu2Mn3In, according to electronegativity size, it is known that Al ratios Cu, Mn are easier to lose electronics, and therefore, Al is Louis
Alkali, Cu, Mn are lewis acid, AlxCu and Al20Cu2Mn3Louis's " acid-base pair " can be regarded as.It is external in melt when being added
When Lewis Acids and Bases are to decomposing, intermetallic compound presoma that can be poor with matrix Presence of an interface is obviously also disturbed and activates
And recurring structure rises and falls, and generates more critical nucleus, makes the concentration of (T+ θ H) combination mutually in the alloy and is evenly distributed density,
Make up to 1/[μm]2More than, here it is Lewis Acids and Bases to that can increase Asia in the disturbance of nanoscale and activation effect
The mechanism of nanoscale particle (T+ θ H) combination phase and the areas nanoscale particle GP, θ ＂, θ ＇ tandem reinforcement phases.
Aluminium alloy melt integrally be used as a rich, high temperature electron system, for electronegativity be higher than its metallic element, be to
Electron, and its active metal element is less than for electronegativity, and be electron acceptor, it is seen that aluminium alloy melt also has Louis
The general general character of this soda acid, itself and the element being added among it can also form broad sense " Lewis Acids and Bases to ", because
The active various elements of adjustment melt chemistry, can be uniformly considered as " lewis acid " or " lewis base " of aluminium alloy by this, when
When using the main group dvielement such as silicon Si of the invention provided, transition group dvielement such as Fe, interior transition dvielement such as Ce, for simplification
Description is also referred to as individual element " Lewis Acids and Bases to " and also to the prominent optimization function to aluminium alloy melt.
To sum up, Lewis Acids and Bases pair of the present invention can show as variform, including metal is formed with ligand binding
Negative ions body, one kind in complicated ligand compound or super large heteropoly compound, main group dvielement, transition group dvielement,
Or more than one mixing.
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 is designed as by weight percentage：Five cyanogen close nickel anion body [Ni (CN)5]3-≤ 0.15%, manganese Mn:≤ 2%, cadmium
Cd:0.05%~0.5%, copper Cu0.5~3% and Cu >=1.5Mn；Lewis Acids and Bases are to total amount 7.0%~9.0%, alloy average crystal grain
120 microns of ＜ is spent, surplus is aluminium Al.Five cyanogen are added and close nickel anion body [Ni (CN)5]3-, improve the strength and stiffness of connecting rod.
Since the mass ratio of copper manganese element in the trunk T-phase of (T+ θ H) combination phase is about 0.8, and in guarantee (T+ θ in alloy
H it also should be ensured that the concentration of (areas GP, θ ＂, θ ＇ or other disc phases) Al-Cu binary disperse phases at different levels while) generation and divide
Cloth density does not reduce, and therefore, copper content design more than more than its a saturation solubility range, while ensureing must have
Manganese exists.Under general condition, (T+ θ H) combines lazy weight 1/[μm] of phase2, so it is difficult to be found, the present invention passes through
The optimization of Lewis Acids and Bases pair, it is ensured that (T+ θ H) combine phase quantity 1/[μm]2More than, depth optimization effect can reach
3/[μm]2More than.
According to material reinforcement theory --- dislocation bypasses and cuts through theory to particle, and the destructive process of material is it first
The concentration stress of middle bulky grain particle, followed by stress in the smaller particle set of particles of secondary level-one, followed by more short grained matter
Point stress, is analogized with secondary；When destroying, the most weak particle of global resistance first destroys, and the strongest particle of global resistance is last
It destroys, only when all particles all never can resist, the destruction of macroscopic view just occurs for material.
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；Due to equiax crystal
It is this because of the free growing endogenetic forming mechanism of liquid internal, change the irregular crystals edge such as plane crystalline substance, dendrite, column crystal
In the unidirectionally extended growth pattern of type wall life core, the certainly export-oriented liquid internal of casting mold cavity, therefore avoid or alleviate alloy
Component segregation, coarse unidirectional, the non-uniform defect of macro property of crystallization, so that some for effectively avoiding or alleviating alloy are common
Defect, such as pin hole, stomata, shrinkage cavity and porosity, segregation, coarse solid solution, high hardness compound, crackle.
According to lewis' theory of acids and bases, aluminum melt is an electron rich high temperature system, that is, belongs to strong lewis base, served as
After the copper manganese of amount is added, since the electronegativity of copper manganese is stronger, the more electron cloud of suction makes the alkali of alloy melt to be formed
Property reduce, surface tension increase, be unfavorable for the generation of critical nucleus；After electron rich substance is added, the acid effect of copper manganese is balanced
It answers, the interfacial tension that original nucleus faces reduces, thus the original nucleus for promoting the trunk T-phase of (T+ θ H) combination phase is grown into
Critical nucleus, to determine that mutually quantity and distribution density significantly improve in the alloy for (T+ θ H) combination.
For the alloy for requiring to reach high-strength performance, Lewis Acids and Bases are not The more the better to additive amount, according to experience, as
Element accounts for Al matrix weight percent, and alternative optimization range is：Li≤0.3%, Si7.5-9.0%, Mg0.3-0.45%,
Ti0.1-0.2%, [Ag (NH3)2]Cl ≤0.03%。
From the foregoing, it can be seen that multifarious Lewis Acids and Bases pair, because having nanoscale superfinishing film micro area in aluminium alloy
It decomposes, disturbance, activation, reconstruct and exclude effect, it is combined to obtain maximum molecule object to making alloy before curing
Self adjustment capability of structure optimization establishes a kind of from precise and tiny structure (Subnano-class or sub-micron grade particle:Scale 10nm~
1 μm of ＜) arrive fine structure (micron particles:1~10 μm or so of scale) crystalline state combination (submicron particles are arrived again:Scale 10
~100 μm or so) self hierarchical adjustment and improve channel, it is insurmountable on the one hand solve alloy phase diagram theory
On the other hand the problem of melt structure and solidification structure optimize solves to alloy refining, rotten, slagging-off, degasification etc.
The following microscopic fields of sub-micron state that conventional technical means is unable to reach, innovative design to aluminium alloy and with aluminium for steel, with light
Strong structure generally substitutes steel weight strong structure, has universal directive significance and industrial value.
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
A kind of preparation method for the aluminum alloy materials substituting QT500 automobile connecting bars, 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 and five cyanogen are added and close nickel anion body [Ni (CN)5]3-, stir, selected Louis be added
This acid-base pair, or selected Lewis Acids and Bases are added to combination, it stirs evenly；
(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) extrusion casint：Refer to pressurizeing in molten condition in aluminium alloy injection running gate system and filling type, solidification and crystallization.
The extrusion casint, 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. taking automatic casting, aluminium alloy is dipped out of stove and pours into ingot-containing tube, ingot-containing tube is moved to mould gate, melt
Extrusion forming when state, pressurize solidification and crystallization.
4. product, natural cooling, 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.
Second part：Specific embodiment
Embodiment 1
1, a kind of aluminium alloy automobile connecting rod material weight percentages of components substituting QT500 is：Cu:2.5%, Mn:0.13%,
Cd:0.02%, different sulphur cyanogen closes iron cation body [Fe（NCS）]2+：0.05%, Li0.1%, Si：7.8%, Mg：0.35%, Ti：
0.13%, [Ag (NH3)2] Cl 0.01%, [Ni (CN)5]3-：0.08%；
2, production procedure：Melting → refining → standing → cast → extrusion forming → die sinking pickup → solid solution → timeliness；
3, melt cast temperature：700 DEG C of ＞；
4, mold preheating temperature：350 DEG C of ＞；
5, filling time：＜ 5s；
6, squeeze pressure is ＞ 12MPa, dwell time：＞ 30s；
7, condition of heat treatment：T7- solid solutions plus overaging；
8, product microstructure index：Metallographic structure is equiax crystal, 70~100 μm of mean grain size, in crystal grain (T+ θ H)
Combine phase amount 2~3/[μm]2；
9, products machinery performance：Power resistance strength 530Mpa, yield strength 470Mpa, elongation after fracture 12%, Brinell hardness
160。
Embodiment 2
1, a kind of aluminium alloy automobile connecting rod material weight percentages of components substituting QT500 is：Cu:2.7%,Mn:0.18%,
Cd:0.05%, Li0.2%, Si：8.5%, Mg：0.42%, Ti：0.17%, [Ag (NH3)2] Cl 0.02%, [Ni (CN)5]3-：
0.13%；
2, specific manufacturing method is same as Example 1；
3, product microstructure index：Metallographic structure is equiax crystal, 80~110 μm of mean grain size, in crystal grain (T+ θ H)
Combine phase amount 1~2/[μm]2；
4, products machinery performance：Power resistance strength 520Mpa, yield strength 450Mpa, elongation after fracture 10%, Brinell hardness
155。
Embodiment 3
1, a kind of aluminium alloy automobile connecting rod material weight percentages of components substituting QT500 is：Cu:1.7%, Mn:0.18%,
Cd:0.05%, [Ag (NH3)2] Cl 0.03%, [Ni (CN)5]3-：0.06%；
2, specific manufacturing method is same as Example 1；
3, product microstructure index：Metallographic structure is equiax crystal, 80~110 μm of mean grain size, in crystal grain (T+ θ H)
Combine phase amount 1~2/[μm]2；
4, products machinery performance：Power resistance strength 510Mpa, yield strength 435Mpa, elongation after fracture 10%, Brinell hardness
145。
Claims (6)
1. a kind of aluminum alloy materials substituting QT500 automobile connecting bars, it is characterised in that：Principal component content is by weight percentage：
Five cyanogen close nickel anion body [Ni (CN)5]3-：0.05%-0.15%, manganese Mn:≤ 2%, cadmium Cd:0.05%~0.5%, copper Cu0.5~
3% and Cu >=1.5Mn；Surplus is aluminium Al；Additive total amount 7.0%~9.0%, 120 microns of alloy mean grain size ＜, alloy are brilliant
Intragranular sub-nanometer (T+ θ H) combination phase amount reaches >=1/square micron, and sub-nanometer (T+ θ H) combines dividing for phase in alloy grain
Subformula is (Al20Cu2Mn3+AlxCu), the thickness that wherein x is less than 2, θ H phases is 20nm, a length of 50nm；The additive is
Metal and one kind in cation body made of ligand binding, complicated ligand compound or super large heteropoly compound, or it is a kind of
A kind of one or more of and aforesaid compound in the above mixing or main group dvielement, transition group dvielement mixes；Described
Complicated ligand compound or super large heteropoly compound, including [Ag (NH3)2]Cl。
2. a kind of aluminum alloy materials substituting QT500 automobile connecting bars according to claim 1, it is characterised in that：Alloy is brilliant
Grain is equiax crystal.
3. a kind of aluminum alloy materials substituting QT500 automobile connecting bars according to claim 2, it is characterised in that：Described
Metal and cation body made of ligand binding：Iron cation body [Fe is closed including different sulphur cyanogen（NCS）]2+。
4. a kind of aluminum alloy materials of replacement QT500 automobile connecting bars according to one of claim 1-3, it is characterised in that：
The additive accounts for Al matrix weight percent, ranging from by element additive amount：Li≤0.3%, Si7.5-9.0%, Mg0.3-
0.45%, Ti0.1-0.2%, [Ag (NH3)2]Cl ≤0.03%。
5. a kind of preparation method of aluminum alloy materials substituting QT500 automobile connecting bars as claimed in claim 4, feature exist
In：It comprises the steps of：(1) within the scope of aforementioned additive, element ratio, one group of substance combination is selected, determines weight ratio, root
According to the alloy total amount that needs are prepared, the weight of each required material is extrapolated；(2) aluminium ingot or molten aluminum are added into smelting furnace
Liquid is heated and is kept the temperature at 700 DEG C or more；(3) manganese Mn, cadmium Cd, copper Cu and five cyanogen are added and close nickel anion body [Ni (CN)5]3-, stir
It mixes, selected additive is added, or selected additive combination is added, stir evenly；(4) then to above-mentioned alloy melt into
Row furnace refining；(5) slagging-off, standing, sampling analysis alloy composition after refining, chemical composition is adjusted extremely according to analysis result
In defined deviation range；To 650 DEG C or more, aluminium alloy is come out of the stove for temperature adjustment, online degasification, slagging-off；(6) extrusion casint：Refer to closing
In golden liquid injection running gate system, pressurizes in molten condition and fill type, solidification and crystallization.
6. a kind of preparation method of aluminum alloy materials substituting QT500 automobile connecting bars according to claim 5, feature exist
In：The extrusion casint, steps are as follows：1. pouring into a mould casting after filtering；2. should preheat mold before casting, sand core is installed, is used
Compressed air blows clean mold cavity；3. taking automatic casting, aluminium alloy is dipped out of stove and pours into ingot-containing tube, ingot-containing tube is moved
Move mould gate, extrusion forming when molten state, pressurize solidification and crystallization；4. die sinking taking-up product, natural cooling, sawing riser,
Polishing overlap；5. appearance quality detection：Rough casting before carrying out presentation quality inspection, should clean out it is smooth, it is non-processing
The dead head in face should be cleaned to cast(ing) surface and flush；6. internal soundness detects；7. solution treatment：Casting is completed into roughing and interior
The blank of outer quality testing is sent into solid solution furnace, carries out 560 DEG C or less solution treatment, is quenched at once after the completion of heat preservation, use water cooling
Or oil cooling；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.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2915391A (en) * | 1958-01-13 | 1959-12-01 | Aluminum Co Of America | Aluminum base alloy |
| CN103131995A (en) * | 2011-12-05 | 2013-06-05 | 贵州铝厂 | Low zinc hot-dipping aluminum alloy plating materials of Cu-Mg and multi-combination metamorphism |
| CN103469024A (en) * | 2013-09-24 | 2013-12-25 | 天津那诺机械制造有限公司 | Special aluminum-alloy material for liquid die-forging molding of aluminum-alloy wheels of heavy-duty vehicle and molding method |
-
2016
- 2016-06-29 CN CN201610492978.3A patent/CN105936991B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2915391A (en) * | 1958-01-13 | 1959-12-01 | Aluminum Co Of America | Aluminum base alloy |
| CN103131995A (en) * | 2011-12-05 | 2013-06-05 | 贵州铝厂 | Low zinc hot-dipping aluminum alloy plating materials of Cu-Mg and multi-combination metamorphism |
| CN103469024A (en) * | 2013-09-24 | 2013-12-25 | 天津那诺机械制造有限公司 | Special aluminum-alloy material for liquid die-forging molding of aluminum-alloy wheels of heavy-duty vehicle and molding method |
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