CN102433469B - Smelting method of aluminium alloy co-dissolved with VC - Google Patents
Smelting method of aluminium alloy co-dissolved with VC Download PDFInfo
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Abstract
The invention relates to an aluminium alloy co-dissolved with VC and a smelting method thereof. The aluminium alloy and the smelting method have the following beneficial effects: 0.8-1.8% of powdery V and 0.8-1.8% of powdery C 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 a kind of aldural, also relate to its preparation method.
Background technology
Tradition Al-Mg-Si-Cu is that the main strengthening phase of alloy is Mg
2Si, a little less than its reinforcement ability than Cu and Zn is, but Cu and Zn are that content is all lower in the alloy at this.
V and C all can form compound with Al, the crystal grain of refinement alloy, promote alloy to form the recrystallized structure of thin crystalline substance, can obtain over-all propertieies such as useful intensity, toughness, plasticity, also can reduce quenching sensitive, reduce the internal structure stress that casting ingot quenching back forms, thereby help the conformal processing of product.
But tradition adds the method that the method for V and C all adopts master alloy directly to add.Because V is a noble metal, and V and C are the high-melting-point elements, the cost of melting Al-V, Al-C master alloy is very high, and also is subjected to the influence of processing condition as the effect that grain-refining agent adds.
When this alloy liquid before cast owing to stirring the inhomogeneous eutectic segregation that causes, concentrate the place in Eutectic Silicon in Al-Si Cast Alloys, the high fragility of hardness is big, the process tool wearing and tearing are big; 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 sticking cutter in man-hour, worsens processing characteristics, can make the distortion of α (Al) sosoloid cause machined surface hickie to occur under the effect of cutting force.When magnesium content was less than 0.6% (massfraction) in ZL108 (ZAlSi12Cu2Mg1) aluminium alloy, hickie also appearred in finished surface easily.
Simultaneously, when adopting this aluminium alloy to cast, the normal appearance mainly contains oxide inclusion, molding material and flux slag inclusion etc. various being mingled with in the foundry goods that casting is finished.Wherein, be mingled with aluminum oxide the most general.Especially in containing the aluminium alloy of Mg, majority is mingled with and is aluminum oxide and magnesian mixture, so in the aluminium alloy smelting process, the content of oxide inclusion is one of important mark matter of reflection aluminium liquid metallurgical quality.
This shows: the forming property of present aluminum alloy materials during except founding is relatively poor, the particularly large-scale ingot blank of foundry goods is not high in the hardening capacity of heat treatment process, tempering resistance is relatively poor and can not satisfy higher mechanical property requirements or some property (as heat-resisting, anti-corrosion) etc., is significant deficiency yet.These defectives make it form the technology breakpoint that is difficult to cross in the process of strong materials of weight such as field of engineering technology instead of steel goods and structure.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of and codissolved aluminium alloy of VC and melting method thereof, can overcome the deficiency of existing aluminium alloy capability, improve its obdurability, plasticity and hardening capacity, for efficient deep processing provides high-end base material.
A kind of and the codissolved aluminium alloy of VC, it is characterized in that by percentage to the quality, comprise 0.2～0.6% Si, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45～0.9% Mg, Zn smaller or equal to 0.1%, Ti smaller or equal to 0.1%, 0.8～1.8% V and 0.19～0.42% C, surplus is Al and unavoidable impurities; The content of described single impurity is no more than 0.05% of total mass per-cent, and content of impurities is no more than 0.15% of total mass per-cent.
The described method with the codissolved aluminium alloy of VC of a kind of melting claim 1 is characterized in that step is as follows:
Step 1: aluminium ingot is added in the smelting furnace heating make it to melt fully, the Si that adds total product mass percent 0.2～0.6% then by prescription, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45～0.9% Mg, Zn smaller or equal to 0.1% and smaller or equal to 0.1% Ti dissolves fully and melts; Described melting process is finished in enclosed environment;
Step 2:, obtain alloy melt 700～1000 ℃ of insulations down;
Step 3: adopt mixed gas that aluminium alloy melt is carried out the degassing and purifying operation, and the VC powder that will account for total product mass percent 0.99～2.22% joins in the aluminium alloy melt with above-mentioned gas in the fluidization mode and mixes, VC is evenly distributed in aluminium alloy melt, and lasting ventilation finish until reaction; Described mixed gas is: nitrogen or rare gas element or nitrogen mix according to arbitrary proportion with rare gas element and obtain;
Step 4: temperature adjustment to 680 after reaction finishes～730 ℃ obtains the aluminium alloy melt that melting is finished.
Aluminium ingot in the step 1 is replaced with molten aluminum liquid.
A kind of with described method of casting with the codissolved aluminium alloy of VC, it is characterized in that: the aluminium alloy melt longshore current groove of claim 2 melting is toppled over come out of the stove, to vertical water cooling casting machine system, the pole that large-scale slab ingot that casting processing ingot blank, particularly cast thickness 500mm are above and diameter 500mm are above.
A kind of with described method of casting with the codissolved aluminium alloy of VC, it is characterized in that: the aluminium alloy melt metaideophone of claim 2 melting is gone 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 technology, the aluminum alloy casting of cast aluminium alloy foundry goods, particularly casting large-scale, thin-walled or complex construction.
Provided by the invention and the codissolved aluminium alloy of VC and melting and castmethod; in wrought aluminium alloy with the VC of Powdered adding 0.99～2.22%; add in the aluminium alloy melt process with protective gas with the fluidization form; have the specific surface area more much bigger than general cake mass; can realize disperseing fast and fully contacting, significantly shorten and disperseed and the uniform time with melt.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 that adds can promote to form interstitial atom and gap mutually, during high temperature in α (Al) sosoloid solubleness big, and very little when room temperature, thereby make alloy have higher heat-treatability matter, after the thermal treatment, its intensity and hardness all have significant improvement.
Make a concrete analysis of as follows:
Without before adding above-mentioned element, except that the common solution that form various elements, also contain compound phase that more following intermetallics form in the melt at this alloy:
Mg
2Si phase, N phase (Al
7Cu
2Fe), α phase (Al
12Fe
3Si), S phase (Al
2CuMg);
These metallic compounds are when melt cools off, because the minimum free energy principle of system, can not stable existence in the crystal grain that forms, will be under the driving that lattice distortion can differ from move and concentrate to crystal boundary, simultaneously, because the saturation solubility of alloying element in aluminum substrate descends along with temperature 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 the intergranular enrichment, be difficult for to each other merging, in microtexture, become thick intergranular compound group, alloy is produced crisp sclerosis influence, worsen the alloy casting forming property, reduce its homogeneity, toughness, solidity to corrosion and through hardening performance.So, when 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 just can have mechanical property and other technical indicator of satisfying the demand after the thermal treatment through " solid solution+timeliness ".
Though, can improve through the thermal treatment of formulation optimization processing and raising alloy property, still still there are a lot of defectives in alloy itself: the insufficient strength height, can not cast big specification type ingot etc.
The present invention is by relatively selecting, the carbide of having developed transition element is handled the mode of melt, by adding 0.8～1.8% V, 0.8～1.8% C element, the atomic state V metal that carbide after the decomposition produces, do not had under the simple substance state between atoms metal with the d//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, with " naked attitude " and a large amount of on every side matrix atom fusions, form solution and metallic compound altogether, and the leading phase when becoming crystallization and grain refining are mutually, also are the High-Temperature Strengthening phases simultaneously.Therefore, carbide has solved refractory metal and dissolved difficult, the difficult problem of uniform distribution in aluminium liquid with the decomposition under the generation high temperature in the fluidization adding melt and the disperse state of formation, has realized the microcosmic homogenizing distribution of lattice distortion energy and the refinement of crystal grain.
Because the Al that C and Al reaction generate
4C
3Be a kind of ionic crystal of complex construction, fusing point reaches 2100 ℃; Atoms metal can be 4,5,6 coordinations in practical structures, and Al-C bond distance exists
Between, the shortest C-C key is
X ray is studied then has single carbon atom with discrete carbanion C in the display structure
4-Form exists; The aluminium carbide particle can reduce the trend of material creep, improves body material hardness; Have strong suction H effect, can effectively remove the atom H of the existence in the melt.
Joining the degree that the carbide in the melt decomposes in addition, change along with the different of the stability of carbide itself and melt temperature, promptly react and have certain reversibility, is a kind of dynamic balance.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 the 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.
The nitrogen that charges in fusion process simultaneously helps aluminium synthetic AlN in 800～1000 ℃ nitrogen atmosphere.Because the AlN that N and Al reaction generates is an atomic crystal, genus quasi-diamond nitride the highlyest is stabilized to 2200 ℃; The room temperature strength height, and intensity is slower with the rising decline of temperature, can effectively improve the hot strength and the resistance to corrosion of alloy; Thermal conductivity is good, and thermal expansivity is little, can improve the body material thermal shock resistance.Therefore, work as N
2When charging into the high temperature aluminium alloys melt, itself has just had the activity that reacts with multiple metallic gold.So the concentration of temperature when suitably regulating the cleaning molten operation and protectiveness nitrogen can be regulated the content of AlN in the melt, this further provides method for the content of regulating transition metal in the melt.
As seen: because the means of using the fluidization carbide to handle in the present invention, the multiple effect of strengthening matrix and crystal grain thinning is integrated, replace master alloy, make aluminium alloy manufacturing concern no longer be limited by the master alloy manufacturer, help creating the green production line of " nearly moulding, short flow process, intensification ", energy-saving and cost-reducing, reduce comprehensive cost; Simultaneously, in heat treatment process, owing to 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, when comparing with similar alloy, can produce thicker blank (bar that sheet material that thickness 500mm is above and diameter 500mm are above) with " casting+heat treatment mode ", (realize " rolling " on the plate of moderate thickness manufacturing technology of thickness 15～200mm) to cast generation at series specification.
Generally speaking, the invention has the beneficial effects as follows:
In molten aluminium, caused multiple grain refining element, particle, thickization that prevents matrix and strengthening phase had good result.In cooled aluminum substrate, caused stable high interstitial atom and gap mutually, become new efficient strengthening phase, the intensity of material and hardness are improved.
The present invention is further described below in conjunction with embodiment.
Embodiment
Embodiment 1:
A kind of and the codissolved aluminium alloy of VC by percentage to the quality, comprise 0.2% Si, 0.35% Fe, 0.1% Cu, 0.1% Mn, 0.1% Cr, 0.45% Mg, 0.1% Zn, 0.1% Ti, 0.8% V, 0.8% C, surplus is Al and unavoidable impurities, 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 the preparation method of described aldural, adds VC in the Combined Processing mode, may further comprise the steps:
Step 1: the component according to described aldural is got the raw materials ready, comprise the Si that accounts for total product mass percent 0.2～0.6%, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45～0.9% Mg, Zn smaller or equal to 0.1%, the Ti smaller or equal to 0.1%;
Step 2: add aluminium ingot or molten aluminum liquid earlier in smelting furnace, heating makes it to melt fully, adds getting the raw materials ready of step 1 earlier by formula rate, makes it to dissolve fully and melt, and 700～1000 ℃ of insulations down, obtains alloy melt after the refining; Melting process is finished in enclosed environment;
Step 3: use the mixed gas of nitrogen or rare gas element or nitrogen and rare gas element arbitrary proportion that alloy melt is carried out the degassing and purifying operation, and lasting ventilation finishes until reaction; The VC powder that will account for total product mass percent 0.8% simultaneously joins in the alloy melt with above-mentioned gas in the fluidization mode; Stir, VC is evenly distributed in alloy melt, and fully react with alloy melt; Leave standstill, temperature adjustment to 680～730 ℃, obtain the aluminium alloy melt that melting is finished.
Embodiment 2:
A kind of and the codissolved aluminium alloy of VC by percentage to the quality, comprise 0.4% Si, 0.3% Fe, 0.08% Cu, 0.08% Mn, 0.06% Cr, 0.7% Mg, 0.07% Zn, 0.05% Ti, 1.3% V, 1.3% C, surplus is Al and unavoidable impurities, 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 the preparation method of described aldural, adds VC in the Combined Processing mode, may further comprise the steps:
Step 1: the component according to described aldural is got the raw materials ready, and comprises the Si that accounts for total product mass percent 0.4%, 0.3% Fe, 0.08% Cu, 0.08% Mn, 0.06% Cr, 0.7% Mg, 0.07% Zn, 0.05% Ti;
Step 2: add aluminium ingot or molten aluminum liquid earlier in smelting furnace, heating makes it to melt fully, adds getting the raw materials ready of step 1 earlier by formula rate, makes it to dissolve fully and melt, and 700～1000 ℃ of insulations down, obtains alloy melt after the refining; Melting process is finished in enclosed environment;
Step 3: use the mixed gas of nitrogen or rare gas element or nitrogen and rare gas element arbitrary proportion that alloy melt is carried out the degassing and purifying operation, and lasting ventilation finishes until reaction; The VC powder that will account for total product mass percent 1.3% simultaneously joins in the alloy melt with above-mentioned gas in the fluidization mode; Stir, VC is evenly distributed in alloy melt, and fully react with alloy melt; Leave standstill, temperature adjustment to 680～730 ℃, obtain the aluminium alloy melt that melting is finished.
Embodiment 3:
A kind of and the codissolved aluminium alloy of VC by percentage to the quality, comprise 0.6% Si, 0.25% Fe, 0.06% Cu, 0.09% Mn, 0.03% Cr, 0.9% Mg, 0.09% Zn, 0.05% Ti, 1.8% V, 1.8% C, surplus is Al and unavoidable impurities, 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 the preparation method of described aldural, adds VC in the Combined Processing mode, may further comprise the steps:
Step 1: the component according to described aldural is got the raw materials ready, and comprises the Si that accounts for total product mass percent 0.6%, 0.25% Fe, 0.06% Cu, 0.09% Mn, 0.03% Cr, 0.9% Mg, 0.09% Zn, 0.05% Ti;
Step 2: add aluminium ingot or molten aluminum liquid earlier in smelting furnace, heating makes it to melt fully, adds getting the raw materials ready of step 1 earlier by formula rate, makes it to dissolve fully and melt, and 700～1000 ℃ of insulations down, obtains alloy melt after the refining; Melting process is finished in enclosed environment;
Step 3: use the mixed gas of nitrogen or rare gas element or nitrogen and rare gas element arbitrary proportion that alloy melt is carried out the degassing and purifying operation, and lasting ventilation finishes until reaction; The VC powder that will account for total product mass percent 1.8% simultaneously joins in the alloy melt with above-mentioned gas in the fluidization mode; Stir, VC is evenly distributed in alloy melt, and fully react with alloy melt; Leave standstill, temperature adjustment to 680～730 ℃, obtain the aluminium alloy melt that melting is finished.
After the aldural liquid of employing the inventive method melting is come out of the stove, carry out the Foundry Production of different goods respectively along following two kinds of flow processs.
Flow process one: the longshore current groove is toppled over and is come out of the stove, to vertical water cooling casting machine system, large-scale slab ingot that casting processing ingot blank, particularly cast thickness 500mm are above and the pole more than the diameter 500mm.
Flow process two: metaideophone is gone in the mold of foundry goods, uses metal mold, sand mold or mixed type casting mode, adopts gravitational casting, pressure die casting or counter-pressure casting technology, the aluminum alloy casting of cast aluminium alloy foundry goods, particularly casting large-scale, thin-walled or complex construction.
Claims (2)
1. method of casting with the codissolved aluminium alloy melt of VC, it is characterized in that by percentage to the quality, comprise 0.2 ~ 0.6% Si, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45 ~ 0.9% Mg, Zn smaller or equal to 0.1%, Ti smaller or equal to 0.1%, 0.8 ~ 1.8% V and 0.19 ~ 0.42% C, surplus is Al and unavoidable impurities; The content of single impurity is no more than 0.05% of total mass per-cent, and content of impurities is no more than 0.15% of total mass per-cent;
The casting step is as follows:
Step 1: aluminium ingot is added in the smelting furnace heating make it to melt fully, the Si that adds total product mass percent 0.2 ~ 0.6% then by prescription, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45 ~ 0.9% Mg, Zn smaller or equal to 0.1% and smaller or equal to 0.1% Ti dissolves fully and melts; Described melting process is finished in enclosed environment;
Step 2:, obtain alloy melt 700～1000 ℃ of insulations down;
Step 3: adopt mixed gas that aluminium alloy melt is carried out the degassing and purifying operation, and the VC powder that will account for total product mass percent 0.99 ~ 2.22% joins in the aluminium alloy melt with above-mentioned gas in the fluidization mode and mixes, VC is evenly distributed in aluminium alloy melt, and lasting ventilation finish until reaction; Described mixed gas is: nitrogen or rare gas element or nitrogen mix according to arbitrary proportion with rare gas element and obtain;
Step 4: temperature adjustment to 680 after reaction finishes～730 ℃ obtains the aluminium alloy melt that melting is finished;
Step 5: the aluminium alloy melt longshore current groove of institute's melting toppled over come out of the stove, to vertical water cooling casting machine system, casting processing ingot blank.
2. method of casting with the codissolved aluminium alloy melt of VC, it is characterized in that by percentage to the quality, comprise 0.2 ~ 0.6% Si, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45 ~ 0.9% Mg, Zn smaller or equal to 0.1%, Ti smaller or equal to 0.1%, 0.8 ~ 1.8% V and 0.19 ~ 0.42% C, surplus is Al and unavoidable impurities; The content of single impurity is no more than 0.05% of total mass per-cent, and content of impurities is no more than 0.15% of total mass per-cent;
The casting step is as follows:
Step 1: molten aluminum liquid is added in the smelting furnace heating make it to melt fully, the Si that adds total product mass percent 0.2 ~ 0.6% then by prescription, Fe smaller or equal to 0.35%, Cu smaller or equal to 0.1%, Mn smaller or equal to 0.1%, the Cr smaller or equal to 0.1%, 0.45 ~ 0.9% Mg, Zn smaller or equal to 0.1% and smaller or equal to 0.1% Ti dissolves fully and melts; Described melting process is finished in enclosed environment;
Step 2:, obtain alloy melt 700～1000 ℃ of insulations down;
Step 3: adopt mixed gas that aluminium alloy melt is carried out the degassing and purifying operation, and the VC powder that will account for total product mass percent 0.99 ~ 2.22% joins in the aluminium alloy melt with above-mentioned gas in the fluidization mode and mixes, VC is evenly distributed in aluminium alloy melt, and lasting ventilation finish until reaction; Described mixed gas is: nitrogen or rare gas element or nitrogen mix according to arbitrary proportion with rare gas element and obtain;
Step 4: temperature adjustment to 680 after reaction finishes～730 ℃ obtains the aluminium alloy melt that melting is finished;
Step 5: the aluminium alloy melt metaideophone of institute's melting is gone 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 technology, the cast aluminium alloy foundry goods.
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