CN103060637B - Metallic hydrogen compound modified high-performance aluminum alloy material and preparation method thereof - Google Patents
Metallic hydrogen compound modified high-performance aluminum alloy material and preparation method thereof Download PDFInfo
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- CN103060637B CN103060637B CN201110324381.5A CN201110324381A CN103060637B CN 103060637 B CN103060637 B CN 103060637B CN 201110324381 A CN201110324381 A CN 201110324381A CN 103060637 B CN103060637 B CN 103060637B
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Abstract
The invention discloses a metallic hydrogen compound modified high-performance aluminum alloy material and a preparation method of the material; the metallic hydrogen compound modified high-performance aluminum alloy material comprises the components by weight percent: less than or equal to 2.0% of Cu, less than or equal to 0.7% of Mn, 1.0-3.0% of Mg, less than or equal to 0.3% of Cr, 3.0-7.0% of Zn, less than or equal to 0.1% of Ti, wherein the content of hydrogen compound MHn modificator accounts for 1ppm-1.0% of the total quantity of furnace charge, and the balance of Al and unavoidable trace impurities, wherein the content of a single impurity element is less than or equal to 0.03%, and the content of the total impurity elements is less than or equal to 0.15%. The metallic hydrogen compound modified high-performance aluminum alloy has a smaller grain structure and higher purity.
Description
Technical field
The present invention relates to a kind of aluminum alloy materials and preparation method thereof, high performance aluminium materials that particularly a kind of metallic hydrogen compound is rotten and preparation method thereof.
Background technology
Metamorphism greatly can improve comprehensive mechanical performance and the chemical stability index of aluminium alloy, sometimes or even subversive.Metamorphic material can be produced and be called alterant.
Alterant nearly all at present all concentrates in a kind of technique means: take aluminium as the master alloy that matrix produces containing alterant element, then when aluminium alloy smelting, master alloy is added in melt.
This process creates two in energy-conservation disadvantageous link: the founding link of the master alloy 1. containing high density alterant element, often need very high temperature (> 1000 DEG C, as Al-Ti-B, Al-RE, Al-Si, Al-Sc, Al-V, Al-Cr, Al-Mn, Al-Co, Al-Ni, Al-W, Al-Zr etc.); 2. add master alloy during aluminium alloy smelting, " dissolving " " dilution " alterant element, then cast.
Concerning aluminium alloy is produced, how said process has been equivalent to " melting-casting " link, and aluminium a large amount of in master alloy only plays the effect storing alterant element, and its energy consumed is invalid completely.
In various aluminium intermediate alloy alterant, most is representational is Al-Ti-B wire rod and aluminium-rare-earth (RE) master alloy.Along with going deep into of research, increasing element is found to have metamorphism, also just creates increasing master alloy.For aluminum alloy smelting factory, in order to be absorbed in the production of terminal alloy product, there is no need special investment and building master alloy production line, and would rather from market purchasing master alloy.So just had the factory of special production aluminium intermediate alloy, and defined industrial scale, current whole world aluminium intermediate alloy industry has reached billions of unit.
Based on the theoretical thinking of aluminium intermediate alloy, the following condition of additive added as alterant limited:
(1) at high temperature chemical composition is constant, has enough stability in molten aluminium;
(2) fusing point of additive should than the height of aluminium;
(3) lattice of additive and aluminium should adapt in scantlings of the structure;
(4) powerful adsorption bond is formed with processed melt atom.
These restricted conditions, the good as if special aluminium intermediate alloy for hot metal element is made to measure, because which limit the connotation and extension of " going bad " concept.
Meanwhile, the effective element in aluminium intermediate alloy alterant is difficult to play one's part to the full.
Although the matrix of master alloy is also aluminium, when producing master alloy, the process of high-melting-point element, indissoluble solution element and aluminium generation alloying is very rambunctious: the segregation of effective element, the scaling loss amount of aluminium increase and a large amount of being mixed into of impurity, all unavoidable.Require that very strict high performance alloys is produced for Light absorbing impurty, the impurity that often alterant is brought into is just enough to make Chemical Composition exceed limited field; Simultaneously, under microstate, a large amount of effective alterant element assembled still is in homojunction colony bulk state, at the temperature of molten aluminum, (< 800 DEG C) cannot dissolve completely and melt at all, the very thin rete in surface is only had to play part metamorphism due to may alloying reaction be produced with aluminium, all the other a large amount of state of aggregations are all how to add just how to exist, and thus metamorphism has a greatly reduced quality.
In actual production, frequent produced problem is that the rotten ability of alterant is unstable, the rate fluctuations scope that alterant adds is large, be not easy accurate perception addition, simultaneously as easy as rolling off a logly in the aluminium intermediate alloy process manufacturing high temperature element be mixed into harmful element, end product quality is had a significant impact.
Summary of the invention
Technical problem to be solved by this invention is, for the defect that aluminum current alloy inoculant and metamorphic mechanism exist, using metallic hydrogen compound fine powder as efficient alterant, join in alloy melt with fluidized regime with protective gas, by discharging the alterant element M of atom or ionic condition with aluminium alloy melt generation chemical reaction or pyrolytic decomposition, be diffused into equably in molten aluminium rapidly, reach efficient, the even object going bad and purify melt, realize the grain refining of matrix and metallic compound phase; And the replacement master alloy in aluminium alloy is produced, cut down the number of intermediate links, energy-saving and cost-reducing.
Technical scheme of the present invention is, by weight percentage, this alloying constituent is Cu :≤2.0%, Mn :≤0.7%, Mg:1.0 ~ 3.0%, Cr :≤0.3%, Zn:3.0 ~ 7.0%, Ti :≤0.1%, hydrogen peroxide adduct MH
nalterant is 1ppm ~ 1.0% of furnace charge total amount, and all the other are Al and inevitable trace impurity, and impurity content is: single≤0.03%, adds up to≤0.15%.
The high performance aluminium materials that a kind of metallic hydrogen compound of the present invention is rotten, in above-mentioned aluminium alloy composition: Si, Fe constituent content meets: Si:0.003 ~ 1.0%, Fe:0.003 ~ 1.0%.
The high performance aluminium materials that a kind of metallic hydrogen compound of the present invention is rotten, above-mentioned metallic hydrogen compound MH
nalterant, wherein M comprises metallic element Li, Na, K, Al, Rb, Sn, Cu, Be, Mg, Ca, Sr, Ba, La, Ce, Eu, Yb or Zr, MH
nalterant is more than one in above metal hydride.
The high performance aluminium materials that a kind of metallic hydrogen compound of the present invention is rotten, metallic hydrogen compound MH
nthe molecular crystal state of aggregation granularity of alterant is 20 ~ 325 orders.
The preparation method of the high performance aluminium materials that a kind of metallic hydrogen compound of the present invention goes bad and preparation method thereof, comprises the steps:
Step one: within the scope of above-mentioned element ratio, a selected group element and metallic hydrogen compound MH
nalterant ratio, then the alloy total amount prepared as required, extrapolate the quality of often kind of required elemental metals, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
Step 2: add aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; Melting process completes in enclosed environment;
Step 3: first add the selected alloying element of step one by formula rate again, make it to dissolve completely and melt, blend melt is stirred;
Step 4: then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent, and stir, melt refining operates in enclosed environment;
Step 5: after refining slagging-off, with protective gas, degasification operation is carried out to melt, make metallic hydrogen compound MH simultaneously
nalterant joins in alloy melt with fluidized regime with protective gas; Stir simultaneously, alterant and alloy melt are fully reacted; Alterant adds complete, continues to pass into protective gas complete to alterant reaction.
Step 6: to leave standstill, temperature adjustment to 700 ~ 800 DEG C, aluminium alloy is toppled over and is come out of the stove, and enters subsequent processing.
The preparation method of the high performance aluminium materials that a kind of metallic hydrogen compound of the present invention goes bad, in step 5, protective gas refers to the mixed gas of nitrogen, argon gas or nitrogen and argon gas.
Compared with prior art, the present invention has following major advantage:
1, have found a kind of efficient alterant newly: metallic hydrogen compound MH
nalterant, change the metamorphic mechanism of conventional aluminum alloy inoculant, metamorphic mechanism is as follows:
MH
n+ e (high temperature) → M (atomic state)+nH (atomic state)
M+Al (liquid) → α (Al) solution altogether → saturated solution → cooling → supersaturated solid solution altogether
M+Al (saturated solution altogether) → M-Al (intermetallic compound)
H (atomic state)+H (molten aluminium) → H
2(gas)
2, metallic hydrogen compound MH
nalterant adds aluminium alloy melt with protective gas fluidization, solves technologic great difficult problem.
3, the modification effect of aluminum alloy modifier is not only increased, for efficient in production, high precision control to create condition, and the element of atomic state that molecular breakdown goes out can squeeze the harmful elements such as H, O in melt, purification melt, thus the effect of alterant and scavenging agent is organically combined.
4, the effective refinement metallic compound crystal grain such as aluminum substrate crystal grain and Fe, Si, significantly improves pure aluminum alloy system intensity and unit elongation performance.
5, replace master alloy, make aluminium alloy manufacturing concern no longer be limited by master alloy manufacturer, be conducive to the intensive production line creating " closely shaping, short route ", energy-saving and cost-reducing, reduce comprehensive cost.
Particularly, the present invention has the following advantages.
1, no longer limit by the conventional need of " under alterant high temperature, chemical composition is constant, has enough stability in molten aluminium "
The present invention adopts metallic hydrogen compound MH
nalterant joins in molten aluminium, and decomposite effective alterant element M with molten aluminium generation chemical reaction, chemical composition changes completely, and this change prerequisite that produced of metamorphism just.
2, no longer by the conventional need restriction of the fusing point of the additive " should than the height of aluminium "
Metallic hydrogen compound MH
nalterant to join in alloy melt with protective gas with fluidized regime to go; according to the size of molecular crystal powder particle; shielding gas amount can be regulated; be unlikely to before making alterant and melt contacts to be heated to its fusing point; even if or reach fusing point; still Stable distritation is in the air-flow of shielding gas, does not affect gas circuit unimpeded and add effect.
3, no longer by the restriction of " lattice of additive and aluminium adapts in scantlings of the structure "
One is due to metallic hydrogen compound MH
nwhat alterant produced with aluminium in the melt is the chemical reaction stronger compared with alloying reaction, molecular crystal pyrolytic decomposition discharges the alloy element of atomic state, there is the seed sphere of action of microcosmic micromicron level (pm), reach to be beyond one's reach when adding pure metal or master alloy microtexture state and nano level (nm) state of aggregation, thus improve mechanical property and the corrosion resistance nature of alloy.
Two is produce crystallization (lattice) structure directing effect: metallic hydrogen compound MH
nalterant decomposes with step type when pyrolytic decomposition, the molecular orbital(MO) generated under its microstate has crystallization guide effect, provide possibility for different-alloy element generates state of aggregation with minimum free energy orientation, and the improvement of state of aggregation is the macro property basis of improving alloy.
Embodiment
Step one: according to the form below selectes every element and material formula, and by the alloy total amount 1000kg prepared, extrapolate the weight of often kind of required material.
Step 2: first add aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; Melting process completes in enclosed environment;
Step 3: first add the selected alloying element of step one by formula rate again, make it to dissolve completely and melt, blend melt is stirred;
Step 4: then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent, and stir, melt refining operates in enclosed environment;
Step 5: after refining slagging-off, with protective gas argon gas, degasification operation is carried out to melt, make carbonyl compound metallic hydrogen compound MH simultaneously
nalterant joins in alloy melt with fluidized regime with protective gas argon gas; Stir simultaneously, alterant and alloy melt are fully reacted; Alterant adds complete, continues to pass into protective gas complete to alterant reaction.
Step 6: to leave standstill, temperature adjustment to 700 ~ 800 DEG C, aluminium alloy is toppled over and is come out of the stove, and enters subsequent processing.
Note: except in step one use material, each material ratio and actual allocate into vary in weight except, all the other steps of each embodiment are all just the same.
Claims (6)
1. the high performance aluminium materials that metallic hydrogen compound is rotten, it is characterized in that: by weight percentage, this alloying constituent is Cu :≤2.0%, Mn :≤0.7%, Mg:1.0 ~ 3.0%, Cr :≤0.3%, Zn:3.0 ~ 7.0%, Ti :≤0.1%, hydrogen peroxide adduct MH
nalterant is 1ppm ~ 1.0% of furnace charge total amount, and all the other are Al and inevitable trace impurity, and impurity content is: single≤0.03%, adds up to≤0.15%.
2. the high performance aluminium materials that a kind of metallic hydrogen compound according to claim 1 is rotten, is characterized in that: in above-mentioned aluminium alloy composition: Si, Fe constituent content meets: Si:0.003 ~ 1.0%, Fe:0.003 ~ 1.0%.
3. the high performance aluminium materials that a kind of metallic hydrogen compound according to claim 1 is rotten, is characterized in that: above-mentioned metallic hydrogen compound MH
nalterant, wherein M comprises metallic element Li, Na, K, Al, Rb, Sn, Cu, Be, Mg, Ca, Sr, Ba, La, Ce, Eu, Yb or Zr, metallic hydrogen compound MH
nalterant is more than one in above metal hydride.
4. the high performance aluminium materials that a kind of metallic hydrogen compound according to claim 1 is rotten, is characterized in that: metallic hydrogen compound MH
nthe molecular crystal state of aggregation granularity of alterant is 20 ~ 325 orders.
5. a preparation method for the high performance aluminium materials that a kind of metallic hydrogen compound as described in Claims 1 to 4 goes bad, is characterized in that: comprise the steps:
Step one: within the scope of above-mentioned element ratio, a selected group element and metallic hydrogen compound MH
nalterant ratio, then the alloy total amount prepared as required, extrapolate the quality of often kind of required elemental metals, establishment alloy production allocation sheet, and get the raw materials ready by allocation sheet choosing foot;
Step 2: add aluminium ingot or molten aluminum liquid in smelting furnace, heating makes it to melt completely and is incubated at 700 ~ 800 DEG C; Melting process completes in enclosed environment;
Step 3: first add the selected alloying element of step one by formula rate again, make it to dissolve completely and melt, blend melt is stirred;
Step 4: then furnace refining is carried out to above-mentioned alloy melt; In alloy melt, add refining agent, and stir, melt refining operates in enclosed environment;
Step 5: after refining slagging-off, with protective gas, degasification operation is carried out to melt, make metallic hydrogen compound MH simultaneously
nalterant joins in alloy melt with fluidized regime with protective gas; Stir simultaneously, alterant and alloy melt are fully reacted; Alterant adds complete, continues to pass into protective gas complete to alterant reaction;
Step 6: to leave standstill, temperature adjustment to 700 ~ 800 DEG C, aluminium alloy is toppled over and is come out of the stove, and enters subsequent processing.
6. the preparation method of high performance aluminium materials that goes bad of a kind of metallic hydrogen compound according to claim 5, it is characterized in that: in step 5, protective gas refers to the mixed gas of nitrogen, argon gas or nitrogen and argon gas.
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| CN1120598A (en) * | 1994-10-12 | 1996-04-17 | 东北轻合金加工厂 | Modification method of High silicon-aluminum alloy |
| CN1196399A (en) * | 1998-02-11 | 1998-10-21 | 国营八一三厂 | Long-acting alterant for casting aluminium alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1120598A (en) * | 1994-10-12 | 1996-04-17 | 东北轻合金加工厂 | Modification method of High silicon-aluminum alloy |
| CN1196399A (en) * | 1998-02-11 | 1998-10-21 | 国营八一三厂 | Long-acting alterant for casting aluminium alloy |
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