CN102433470B - Aluminium alloy co-dissolved with TiAlN and CaH3 powder and smelting method - Google Patents
Aluminium alloy co-dissolved with TiAlN and CaH3 powder and smelting method Download PDFInfo
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Abstract
The invention relates to an aluminium alloy co-dissolved with TiAlN and CaH3 powder and a smelting method. The aluminium alloy and the smelting method have the following beneficial effects: 0.6-1.5% of powdery TiAlN and 0.6-1.5% of powdery CaH3 are added to the wrought aluminium alloy, have specific surface areas much bigger than the specific surface areas of the common massive substances in the process of being added to the aluminium alloy melt in a fluidized form along with the protective gas and can realize rapid dispersion and fully contact with the smelt, thus obviously shortening the dispersion and homogenization time; meanwhile, by adopting the high strength aluminium alloy, the nuclei of heterogeneous nucleation can be effectively added in the alloy solidification process in the casting process, thus achieving the effect of grain refinement and improving the alloy strength; the added elements can promote formation of interstitial atoms and interstitial phases and have high solubility in alpha (Al) solid solution at high temperature and low solubility at room temperature, thus ensuring the alloy to have higher heat-treatable property; and after heat treatment, the hardness and strength of the alloy are improved to a great extent.
Description
Technical field
The present invention relates to one and roll aldural with casting generation, also relate to its melting method.
Background technology
The aluminium alloy that deep processing is used often needs to be first cast as large-scale ingot blank, as slab ingot, pole etc., again by means such as rolling, extruding, forgings, be processed into various finished products, these processes substantially all will with heat treatment phase combination, if to the finished product that can directly use, also will be through operations such as over-segmentation, surface working, Passivation Treatment.These processing means, need aluminum alloy materials itself to possess good deep processing performance, comprise castability, press working deformation performance, heat treatment reinforcement performance, corrosion resistance, antifatigue destructive characteristics, surface working and coating property etc.Wherein, founding performance is the basis of aluminium alloy deep processing performance.Large-scale ingot blank, especially slab ingot more than thickness 500mm, slab and pole more than diameter 500mm, can be the representative base material of Large Efficient deep processing, and be prefabricated into large-scale ingot blank, be also the first technology critical point whether test aluminum alloy materials itself is applicable to carrying out deep processing.
When in Al-Si-Cu line aluminium alloy due to composition and pouring technology improper, easily form high hardness compound.Especially be less than 12% (massfraction) for silicon content, the content of Mn+Fe during higher than 0.8% (massfraction), is very easy to generate
al 12 si (FeMn) 3 compound.Because the hardness after this aluminium alloy shaping is higher, when mechanical workout, tool wear is serious, the white light tone hard point that the surperficial naked eyes after processing are heaved as seen, and microscopic examination hard point is bone shape or irregular particle shape.Composition through this hard point of power spectrum composition measurement consists of Al-Si-Mn-Fe, its form very easily with alloy in primary silicon obscure mutually.When the part having after the aluminium alloy of this hard point compound is shaped, not only poor in processability, and have a strong impact on the roughness of finished surface and the quality of anodic film.
Because the one-tenth branch that in alloying constituent or compound, density is large is deposited in foundry goods bottom, on the little composition of density, float on top.For example add this refractory metal of Ti and Al for crystal grain thinning and form dystectic flaky compound Al
3ti can early crystallize out from aluminium alloy, when growing up to the gravity segregation that just easily sinks to producing local code when larger, when segregation is more serious, can on foundry goods fracture, see the compound of the white bright ash of surfacing, primary silicon thick in hypereutectic Al-Si aluminium alloy also easily forms segregation because density is less.
In addition when this aluminium alloy before cast owing to stirring the inhomogeneous eutectic segregation that causes, concentrate place in Eutectic Silicon in Al-Si Cast Alloys, the high fragility of hardness is large, process tool wearing and tearing are large; The position that Eutectic Silicon in Al-Si Cast Alloys is few forms α (Al) sosoloid soft spots, and intensity is low, adds not only sticky cutter in man-hour, worsens processing characteristics, can make the distortion of α (Al) sosoloid cause machined surface to occur hickie under the effect of cutting force.In the time that in ZL108 (ZAlSi12Cu2Mg1) aluminium alloy, magnesium content is less than 0.6% (massfraction), also easily there is hickie in finished surface.
Meanwhile, in the time adopting this aluminium alloy to cast, in the foundry goods of having cast, normal appearance, mainly contains oxide inclusion, molding material and flux mixture etc. at various being mingled with.Wherein, be mingled with aluminum oxide the most general.Especially containing in the aluminium alloy of Mg, majority is mingled with for aluminum oxide and magnesian mixture, so in aluminium alloy smelting process, the content of oxide inclusion is one of important mark matter of reflection aluminium liquid metallurgical quality.
As can be seen here: the forming property of current aluminum alloy materials during except the large-scale ingot blank of founding is poor, large-scale ingot blank is not high in the hardening capacity of heat treatment process, tempering resistance is poor and can not meet higher mechanical property requirements or some property (as heat-resisting, anti-corrosion) etc., is significant deficiency yet.These defects make it in the process of the strong materials of weight such as field of engineering technology instead of steel goods and structure, form the technology breakpoint that is difficult to leap.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of and TiAlN and CaH
3powder is molten aluminium alloy and melting method thereof altogether, can overcome the deficiency of existing aluminium alloy capability, improves its obdurability, plasticity and hardening capacity, for efficient deep processing provides high-end base material.
One and TiAlN and CaH
3powder is molten aluminium alloy altogether, it is characterized in that by percentage to the quality, comprise 1.0～1.7% Si, be less than or equal to 0.5% Fe, 0.15～0.4% Cu, 0.4～1.0% Mn, be less than or equal to 0.1% Cr, 0.5～1.2% Mg, is less than or equal to 0.25% Zn, 0.6～1.5% Ti, 0.18～0.44% N and 0.88～2.19% Ca, surplus is Al and inevitable impurity, and the content of single contaminant is no more than 0.05% of total mass per-cent, and total impurities is no more than 0.15% of total mass per-cent.
One and TiAlN and CaH
3powder is the melting method of molten aluminium alloy altogether, it is characterized in that step is as follows:
Step 1: add heating in smelting furnace to make it to melt completely aluminium ingot, then add total product mass percent to account for the Si of total product mass percent 1.0～1.7% by formula, be less than or equal to 0.5% Fe, 0.15～0.4% Cu, 0.4～1.0% Mn, be less than or equal to 0.1% Cr, 0.5～1.2% Mg and be less than or equal to 0.25% Zn, makes it dissolve completely and melt; Described melting process completes in enclosed environment;
Step 2: insulation at 700～1000 DEG C, obtains alloy melt;
Step 3: adopt mixed gas to carry out degassing and purifying operation to aluminium alloy melt, and will account for the TiAlN of total product mass percent 1.12～2.78% and 0.92～2.28% CaH
3powder joins in aluminium alloy melt and mixes with above-mentioned gas in fluidization mode, makes TiAlN and CaH
3in aluminium alloy melt, be evenly distributed, and continue ventilation until react complete; Described mixed gas is: nitrogen or rare gas element or nitrogen and rare gas element are mixed to get according to arbitrary proportion;
Step 4: reaction finishes rear temperature adjustment to 680～730 DEG C, obtains the aluminium alloy melt that melting completes.
Aluminium ingot in step 1 is replaced with molten aluminum liquid.
A kind of by described and TiAlN and CaH
3the powder method that molten aluminium alloy is cast altogether, it is characterized in that: the aluminium alloy melt of claim 2 melting is toppled over and come out of the stove along chute, to vertical water cooling casting machine system, casting processing ingot blank, particularly large-scale slab ingot more than cast thickness 500mm and pole more than diameter 500mm.
A kind of by described and TiAlN and CaH
3the powder method that molten aluminium alloy is cast altogether, it is characterized in that: the aluminium alloy melt metaideophone of claim 2 melting is entered in the mold of foundry goods, use metal mold, sand mold or mixed type casting mode, adopt gravitational casting, pressure die casting or counter-pressure casting technique, the aluminum alloy casting of Casting Aluminum Alloy Based, particularly casting large-scale, thin-walled or complex construction.
Provided by the invention can with TiAlN and CaH
3altogether molten aluminium alloy and melting method thereof of powder, in wrought aluminium alloy with Powdered 1.12～2.78% TiAlN and 0.92～2.28% the CaH of adding
3, add in aluminium alloy melt process with protective gas with fluidization form, there is the specific surface area more much bigger than general cake mass, can realize and disperse fast and fully contact with melt, significantly shorten and disperseed and the uniform time.Adopt aldural of the present invention simultaneously in castingprocesses, can in alloy graining process, effectively increase heterogeneous forming core core, thereby reach the effect of grain refining, strengthen alloy strength; And the element adding can promote to form interstitial atom and gap phase, when high temperature, in α (Al) sosoloid, solubleness is large, and very little in the time of room temperature, thereby makes alloy have higher heat-treatability matter, after thermal treatment, its intensity and hardness all have significant improvement.
Make a concrete analysis of as follows:
Without before adding above-mentioned element, in melt, except forming the common solution of various elements, also contain the Compound Phase that more following intermetallics form at this alloy:
θ phase (CuAl
2), Mg
2si phase, N phase (Al
7cu
2fe), α phase (Al
12fe
3si), S phase (Al
2cuMg);
These metallic compounds are in the time of melt cooling, due to the minimum free energy principle of system, can not stable existence in the crystal grain forming, to under the driving that can differ from lattice distortion, move and concentrate to crystal boundary, simultaneously, because the saturation solubility of alloying element in aluminum substrate is along with temperature declines and significantly reduces, so cooling along with melt, oversaturated melt is constantly separated out the intermetallic compound that is rich in alloying element, these compounds are in intergranular enrichment, be difficult for to each other merging, in microtexture, become thick intergranular compound group, alloy produces crisp hardening effect, worsen alloy casting forming property, reduce its homogeneity, toughness, solidity to corrosion and through hardening performance.So, in the time that alloy graining becomes the basic structure of supersaturated solid solution matrix+intergranular metallic compound, be commonly referred to pure as-cast structure, the alloy with this tissue must be through just having mechanical property and other technical indicator of satisfying the demand after the thermal treatment of " solid solution+timeliness ".
Although, can improve through the thermal treatment of formulation optimization processing and raising alloy property, still still there are a lot of defects in alloy itself: insufficient strength is high, can not cast large specification type ingot etc.
The present invention passes through alternative, the nitride of having developed transition element is processed the mode of melt, by adding 0.6～1.5% Ti, 0.6～1.5% N, 0.6～1.5% Ca element, the atomic state M metal that nitride after decomposition produces, do not have under simple substance state between atoms metal with the d/f/s electronics potential barrier that the lattice energy of tightly packed generation between the powerful metal bond energy that produces and similar atom forms of combining closely, merge with " naked state " and a large amount of around matrix atoms, form solution and metallic compound altogether, and leading phase and grain refining phase while becoming crystallization, also be High-Temperature Strengthening phase simultaneously.Therefore, nitride adds the decomposition that produces in melt under high temperature and the disperse state of formation with fluidization, solved refractory metal in aluminium liquid, dissolve difficult, be uniformly distributed difficult problem, realized lattice distortion can microcosmic homogenizing distribute and the refinement of crystal grain.
The nitrogen being filled with in fusion process in addition, is conducive to aluminium synthetic AlN in the nitrogen atmosphere of 800～1000 DEG C.Be atomic crystal because N reacts the AlN generating with Al, belong to quasi-diamond nitride, be the highlyest stabilized to 2200 DEG C; Room temperature strength is high, and the rising of intensity temperature decline is slower, can effectively carry heavy alloyed hot strength and resistance to corrosion; Thermal conductivity is good, and thermal expansivity is little, can improve body material thermal shock resistance.Therefore, work as N
2while being filled with high temperature aluminium alloys melt, itself has just had the activity reacting with various metals gold.So the concentration of the temperature while suitably regulating cleaning molten operation and protectiveness nitrogen, the content of AlN in adjustable melt, this is further for the content that regulates transition metal in melt provides method.
Join in addition the degree that nitride in melt decomposes, change along with the stability of nitride itself and the difference of melt temperature, i.e. reaction has certain reversibility, is a kind of balance dynamically.The saturation solubility of most of transition element in molten aluminium is less, and the maximum solid solution degree of dechromisation, titanium, vanadium, zirconium occurs in outside peritectic temperature, and the maximum solid solution degree of other elements all occurs in eutectic temperature; Solubleness at room temperature, is all less than 0.1%wt.
Visible: owing to using in the present invention the means of fluidization nitride processing, the multi-effect of strengthening matrix and crystal grain thinning is integrated, replace master alloy, make aluminium alloy manufacturing concern no longer be limited by master alloy manufacturer, be conducive to create the Green line of " nearly moulding, short flow process, intensive ", energy-saving and cost-reducing, reduce comprehensive cost; Simultaneously, in heat treatment process, owing to having formed excellent material microstructure, the unrelieved stress of ingot blank is less, therefore can significantly improve thermal treatment usefulness, improve the hardening capacity of ingot blank, in the time comparing with similar alloy, can produce thicker blank (sheet material more than thickness 500mm and bar more than diameter 500mm) with " casting+heat treatment mode ", in the plate of moderate thickness manufacturing technology of series specification (thickness 15～200mm), realize " rolling to cast generation ".
Generally speaking, the invention has the beneficial effects as follows:
In molten aluminium, cause multiple grain refining element, particle, the coarsening that prevents matrix and strengthening phase has been had to good result.In cooled aluminum substrate, cause the high interstitial atom of stability and gap phase, become new efficient strengthening phase, the intensity of material and hardness are improved.
Below in conjunction with embodiment, the present invention is further described.
Embodiment
Embodiment 1:
One and TiAlN and CaH
3powder is molten aluminium alloy altogether, by percentage to the quality, comprises 1.0% Si, 0.5% Fe, 0.15% Cu, 0.4% Mn, 0.1% Cr, 0.5% Mg, 0.25% Zn, 0.6% Ti, 0.6% N, 0.6% Ca, surplus is Al and inevitable impurity, and the content of every kind of impurity is no more than 0.05% of total mass per-cent, and the content of all impurity is no more than 0.15% of total mass per-cent.
The present invention also provides described and TiAlN and CaH
3powder is the preparation method of molten aluminium alloy altogether, adds TiAlN and CaH in Combined Processing mode
3, comprise the following steps:
Step 1: the component according to described aldural is got the raw materials ready, comprises the Si that accounts for total product mass percent 1.0%, 0.5% Fe, 0.15% Cu, 0.4% Mn, 0.1% Cr, 0.5% Mg, 0.25% Zn;
Step 2: first add aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt completely, first adds getting the raw materials ready of step 1 by formula rate, makes it to dissolve completely and melt, and after refining, insulation at 700～1000 DEG C, obtains alloy melt; Melting process completes in enclosed environment;
Step 3: use the mixed gas alloy melt of nitrogen or rare gas element or nitrogen and rare gas element arbitrary proportion to carry out degassing and purifying operation, and continue ventilation until react complete; The TiAlN of total product mass percent 0.6%, 0.6～1.5% CaH will be accounted for simultaneously
3powder joins in alloy melt with above-mentioned gas in fluidization mode; Stir, make TiAlN and CaH
3in alloy melt, be evenly distributed, and fully react with alloy melt; Standing, temperature adjustment to 680～730 DEG C, obtain the aluminium alloy melt that melting completes.
Embodiment 2:
One and TiAlN and CaH
3powder is molten aluminium alloy altogether, by percentage to the quality, comprises 1.3% Si, 0.4% Fe, 0.28% Cu, 0.7% Mn, 0.08% Cr, 0.8% Mg, 0.2% Zn, 1.1% Ti, 1.1% N, 1.1% Ca, surplus is Al and inevitable impurity, and the content of every kind of impurity is no more than 0.05% of total mass per-cent, and the content of all impurity is no more than 0.15% of total mass per-cent.
The present invention also provides described and TiAlN and CaH
3powder is the preparation method of molten aluminium alloy altogether, adds TiAlN and CaH in Combined Processing mode
3, comprise the following steps:
Step 1: the component according to described aldural is got the raw materials ready, comprises the Si that accounts for total product mass percent 1.3%, 0.4% Fe, 0.28% Cu, 0.7% Mn, 0.08% Cr, 0.8% Mg, 0.2% Zn;
Step 2: first add aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt completely, first adds getting the raw materials ready of step 1 by formula rate, makes it to dissolve completely and melt, and after refining, insulation at 700～1000 DEG C, obtains alloy melt; Melting process completes in enclosed environment;
Step 3: use the mixed gas alloy melt of nitrogen or rare gas element or nitrogen and rare gas element arbitrary proportion to carry out degassing and purifying operation, and continue ventilation until react complete; The TiAlN of total product mass percent 1.1%, 1.1% CaH will be accounted for simultaneously
3powder joins in alloy melt with above-mentioned gas in fluidization mode; Stir, make TiAlN and CaH
3in alloy melt, be evenly distributed, and fully react with alloy melt; Standing, temperature adjustment to 680～730 DEG C, obtain the aluminium alloy melt that melting completes.
Embodiment 3:
One and TiAlN and CaH
3powder is molten aluminium alloy altogether, by percentage to the quality, comprises 1.7% Si, 0.3% Fe, 0.4% Cu, 1.0% Mn, 0.06% Cr, 1.2% Mg, 0.18% Zn, 1.5% Ti, 1.5% N, 1.5% Ca, surplus is Al and inevitable impurity, and the content of every kind of impurity is no more than 0.05% of total mass per-cent, and the content of all impurity is no more than 0.15% of total mass per-cent.
The present invention also provides described and TiAlN and CaH
3powder is the preparation method of molten aluminium alloy altogether, adds TiAlN and CaH in Combined Processing mode
3, comprise the following steps:
Step 1: the component according to described aldural is got the raw materials ready, comprises the Si that accounts for total product mass percent 1.0～1.7%, is less than or equal to 0.5% Fe, 0.15～0.4% Cu, 0.4～1.0% Mn, is less than or equal to 0.1% Cr, 0.5～1.2% Mg, is less than or equal to 0.25% Zn;
Step 2: first add aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt completely, first adds getting the raw materials ready of step 1 by formula rate, makes it to dissolve completely and melt, and after refining, insulation at 700～1000 DEG C, obtains alloy melt; Melting process completes in enclosed environment;
Step 3: use the mixed gas alloy melt of nitrogen or rare gas element or nitrogen and rare gas element arbitrary proportion to carry out degassing and purifying operation, and continue ventilation until react complete; The TiAlN of total product mass percent 1.5%, 0.6～1.5% CaH will be accounted for simultaneously
3powder joins in alloy melt with above-mentioned gas in fluidization mode; Stir, make TiAlN and CaH
3in alloy melt, be evenly distributed, and fully react with alloy melt; Standing, temperature adjustment to 680～730 DEG C, obtain the aluminium alloy melt that melting completes.
After the aldural liquid of employing the inventive method melting is come out of the stove, carry out respectively the Foundry Production of different goods along following two kinds of flow processs.
Flow process one: topple over and come out of the stove along chute, to vertical water cooling casting machine system, casting processing ingot blank, particularly large-scale slab ingot more than cast thickness 500mm and pole more than diameter 500mm.
Flow process two: metaideophone enters in the mold of foundry goods, is used metal mold, sand mold or mixed type casting mode, adopts gravitational casting, pressure die casting or counter-pressure casting technique, the aluminum alloy casting of Casting Aluminum Alloy Based, particularly casting large-scale, thin-walled or complex construction.
Claims (5)
1. one kind and TiAlN and CaH
3altogether molten aluminium alloy of powder, is characterized in that being 1.0～1.7% Si by percentage to the quality, is less than or equal to 0.5% Fe, 0.15～0.4% Cu, 0.4～1.0% Mn, is less than or equal to 0.1% Cr, 0.5～1.2% Mg, be less than or equal to 0.25% Zn, 0.6～1.5% Ti, 0.18～0.44% N and 0.88～2.19% Ca, surplus is Al and inevitable impurity, the content of single contaminant is no more than 0.05% of total mass per-cent, and total impurities is no more than 0.15% of total mass per-cent.
2. an one claimed in claim 1 and TiAlN and CaH
3powder is the melting method of molten aluminium alloy altogether, it is characterized in that step is as follows:
Step 1: add heating in smelting furnace to make it to melt completely aluminium ingot, then add the Si of total product mass percent 1.0～1.7% by formula, be less than or equal to 0.5% Fe, 0.15～0.4% Cu, 0.4～1.0% Mn, be less than or equal to 0.1% Cr, 0.5～1.2% Mg and be less than or equal to 0.25% Zn, makes it dissolve completely and melt; Described melting process completes in enclosed environment;
Step 2: insulation at 700～1000 DEG C, obtains alloy melt;
Step 3: adopt gas to carry out degassing and purifying operation to aluminium alloy melt, and will account for the TiAlN of total product mass percent 1.12～2.78% and 0.92～2.28% CaH
3powder joins in aluminium alloy melt and mixes with above-mentioned gas in fluidization mode, makes TiAlN and CaH
3in aluminium alloy melt, be evenly distributed, and continue ventilation until react complete; Described gas is: nitrogen or rare gas element or nitrogen and rare gas element are mixed to get according to arbitrary proportion;
Step 4: reaction finishes rear temperature adjustment to 680～730 DEG C, obtains the aluminium alloy melt that melting completes.
3. melting method according to claim 2, is characterized in that: the aluminium ingot in step 1 is replaced with molten aluminum liquid.
4. one kind by claimed in claim 2 and TiAlN and CaH
3the powder method that molten aluminium alloy is cast altogether, is characterized in that: the aluminium alloy melt of claim 2 melting toppled over and come out of the stove along chute, and to vertical water cooling casting machine system, casting processing ingot blank.
5. one kind by claimed in claim 2 and TiAlN and CaH
3the powder method that molten aluminium alloy is cast altogether, it is characterized in that: the aluminium alloy melt metaideophone of claim 2 melting is entered in the mold of foundry goods, use metal mold, sand mold or mixed type casting mode, adopt gravitational casting, pressure die casting or counter-pressure casting technique, Casting Aluminum Alloy Based.
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|---|---|---|---|
| CN201110421072.XA CN102433470B (en) | 2011-12-15 | 2011-12-15 | Aluminium alloy co-dissolved with TiAlN and CaH3 powder and smelting method |
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| CN102433470B true CN102433470B (en) | 2014-06-18 |
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