CN1436870A - Al-Zn-Mg-Er rare earth aluminium alloy - Google Patents
Al-Zn-Mg-Er rare earth aluminium alloy Download PDFInfo
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- CN1436870A CN1436870A CN 03119119 CN03119119A CN1436870A CN 1436870 A CN1436870 A CN 1436870A CN 03119119 CN03119119 CN 03119119 CN 03119119 A CN03119119 A CN 03119119A CN 1436870 A CN1436870 A CN 1436870A
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Abstract
The present invention relates to metal alloy technology. The key of the present invention is the addition of RE element Er in the experiment determined amount 0.1-0.7 wt% into the alloy. During the preparation process of the Al-Zn-Mg-Er alloy, Al-Er intermediate alloy through vacuum smelting is added into Al-Zn-Mg alloy. The addition of Er can fine obviously the alloy grains, raise alloy strength greatly and suppress re-crystallization. In addition, Er is relatively cheap and its addition has no significant increase in production cost. On the basis of Al-Zn-Mg alloy as one of the typical industrial Al alloy, one series of Er containing Al-RE alloy may be developed and used in astronautics, aeronautics, traffic and other fields.
Description
One, technical field
The invention belongs to field of metal alloy technology.
Two, background technology
The result of literature survey shows, external research aspect rare earth aluminium alloy seldom, only report also is only limited to the research that contains Sc aluminium alloy aspect.Domestic development and application to rare earth aluminium alloy starts to walk early, later 1970s begins broad scale research and exploitation rare earth aluminium alloy, it is at present domestic that metamorphism in the Al-Si alloy compares deep research to various rare earth elements, application and rare earth the aspects such as application in architectural aluminum section of rare earth in electrician's aluminium alloy also obtained good effect, but, then mainly concentrate on La, Ce, Y and the mishmetal the particularly research of wrought aluminium alloy of other aluminium alloy.This research group finds that rare earth Er has significant strengthening effect to fine aluminium, its strengthening effect mainly from the Er element to the refinement of Al matrix and the equally distributed tiny Al that forms at intragranular
3The Er phase.Al
3Er and Al
3Sc and Al
3The Zr structure is identical, belong to Pm3m spacer (simple cube), lattice parameter and Al matrix are very approaching, this shows, Er is that (Sc is micro-to the aluminium alloy modifying function to the trace alloying element that can effectively improve aluminium alloy capability behind Sc, but the price of Sc is very expensive, and the price of Er only be Sc 1/40).The present invention further adds rare earth Er in the Al-Zn-Mg alloy to, found that the remarkable refinement alloy grain of adding energy of Er, increases substantially alloy strength, suppresses recrystallize; Although the Sc element added to also this effect in the Al-Zn-Mg alloy, Sc costs an arm and a leg, and adds Sc in the aluminium alloy and will increase substantially production cost; And the price comparison of Er is cheap, adds the Er element and can not increase substantially production cost in aluminium alloy, therefore is highly suitable in the industrial production and applies.The Al-Zn-Mg alloy is a kind of typical industry aluminium alloy, and it is studied the novel rare-earth aluminium alloy that can develop a series of Er of containing, is widely used in numerous areas such as Aeronautics and Astronautics, communications and transportation.Relevant Al-Zn-Mg-Er alloy is not seen any report so far as yet.
Three, summary of the invention
The objective of the invention is to seek a kind of suitable rare earth element, join in the Al-Zn-Mg alloy, can effective microalloying effect take place, thereby improve the strength property of alloy with alloy with appropriate vol.
Al-Zn-Mg-Er alloy provided by the present invention, it is characterized in that (the weight percentage 6.0% of Zn in the Al-Zn-Mg alloy described here toward Al-Zn-Mg, the weight percentage of Mg is 2.0%, Al is a surplus, added 0.1～0.7% (weight percent Wt%) rare earth element er down together down together).
The preferable content range of above-described rare earth Er is: 0.25～0.55%.
Adopt traditional ingot metallurgy legal system to be equipped with the Al-Zn-Mg-Er alloy, specifically in two steps: be that raw material prepares the Al-Er master alloy through vacuum casting at first with pure Al and pure Er; Then with pure Al, pure Mg, pure Zn and Al-Er master alloy are raw material melting in crucible electrical resistance furnace, pour into preparation Al-Zn-Mg-Er alloy in the punching block again.
Among the present invention, because the adding of rare earth Er, make the remarkable refinement of Al-Zn-Mg alloy grain, intensity increases substantially, under the constant substantially prerequisite of unit elongation (δ) with tensile strength of alloys (σ
b) and yield strength (σ
0.2) improve about 100MPa; Simultaneously, rare earth Er can also significantly suppress the Al-Zn-Mg alloy recrystallization, and the initial recrystallization temperature of alloy is improved 50 ℃, and the end of a period recrystallization temperature improves 80 ℃.
Four, description of drawings
Fig. 1: the as-cast metallographic structure of alloy, wherein Fig. 1 (a) is the Al-Zn-Mg alloy, Fig. 1 (b) is the Al-Zn-Mg-0.4Er alloy;
Fig. 2: cold rolling attitude tensile property of Al-Zn-Mg-Er alloy and Er relation with contents curve;
Fig. 3: Al-Zn-Mg-Er alloy (+120 ℃/30h of 470 ℃/0.5h quenching timeliness) tensile property and Er relation with contents curve;
Fig. 4: Al-Zn-Mg and Al-Zn-Mg-0.4Er hardness of alloy and annealing temperature relation curve;
Fig. 5 is the metallographic microstructure after Al-Zn-Mg and Al-Zn-Mg-0.4Er anneal under differing temps, wherein Fig. 5 (a) is 325 ℃/1h of an Al-Zn-Mg alloy annealed state tissue, Fig. 5 (b) is 325 ℃/1h of an Al-Zn-Mg-0.4Er alloy annealed state tissue, Fig. 5 (c) is 450 ℃/1h of an Al-Zn-Mg alloy annealed state tissue, and Fig. 5 (d) is 450 ℃/1h of an Al-Zn-Mg-0.4Er alloy annealed state tissue.
Five, embodiment
Comparative Examples: adopt the ingot metallurgy legal system to be equipped with Al-Zn-Mg alloy (the 0# alloy in the table 1), raw materials used is high-purity Al (purity is 99.99%), technical pure Mg (purity is 99.9%), technical pure Zn (purity is 99.9%).At first rafifinal 1612.4 grams are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal melts fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes.
Example 1: adopt the ingot metallurgy method to prepare the Al-Zn-Mg-Er alloy, be raw material at first with high-purity Al (purity reaches 99.99%) and pure Er (purity reaches 99.9%), employing is carried out melting to the method for mixing (consolute method) in vacuum induction furnace, casting, preparation Al-6.2Er master alloy.Then rafifinal 1584.9 grams and 27.4 gram Al-6.2Er master alloys are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal and Al-6.2Er master alloy melt fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes, the size of each ingot casting is 120 * 90 * 32 (mm
3).
Example 2: adopt the ingot metallurgy method to prepare the Al-Zn-Mg-Er alloy, be raw material at first with high-purity Al (purity reaches 99.99%) and pure Er (purity reaches 99.9%), employing is carried out melting to the method for mixing (consolute method) in vacuum induction furnace, casting, preparation Al-6.2Er master alloy.Then rafifinal 1543.7 grams and 68.5 gram Al-6.2Er master alloys are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal and Al-6.2Er master alloy melt fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes, the size of each ingot casting is 120 * 90 * 32 (mm
3).
Example 3: adopt the ingot metallurgy method to prepare the Al-Zn-Mg-Er alloy, be raw material at first with high-purity Al (purity reaches 99.99%) and pure Er (purity reaches 99.9%), employing is carried out melting to the method for mixing (consolute method) in vacuum induction furnace, casting, preparation Al-6.2Er master alloy.Then rafifinal 1502.5 grams and 109.7 gram Al-6.2Er master alloys are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal and Al-6.2Er master alloy melt fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes, the size of each ingot casting is 120 * 90 * 32 (mm
3).
Example 4: adopt the ingot metallurgy method to prepare the Al-Zn-Mg-Er alloy, be raw material at first with high-purity Al (purity reaches 99.99%) and pure Er (purity reaches 99.9%), employing is carried out melting to the method for mixing (consolute method) in vacuum induction furnace, casting, preparation Al-6.2Er master alloy.Then rafifinal 1461.2 and 150.8 gram Al-6.2Er master alloys are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal and Al-6.2Er master alloy melt fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes, the size of each ingot casting is 120 * 90 * 32 (mm
3).
Example 5: adopt the ingot metallurgy method to prepare the Al-Zn-Mg-Er alloy, be raw material at first with high-purity Al (purity reaches 99.99%) and pure Er (purity reaches 99.9%), employing is carried out melting to the method for mixing (consolute method) in vacuum induction furnace, casting, preparation Al-6.2Er master alloy.Then rafifinal 1420.1 grams and 191.9 gram Al-6.2Er master alloys are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal and Al-6.2Er master alloy melt fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes, the size of each ingot casting is 120 * 90 * 32 (mm
3).Execute example 1: adopt the ingot metallurgy method to prepare the Al-Zn-Mg-Er alloy, be raw material at first with high-purity Al (purity reaches 99.99%) and pure Er (purity reaches 99.9%), employing is carried out melting to the method for mixing (consolute method) in vacuum induction furnace, casting, preparation Al-6.2Er master alloy.Then rafifinal 1584.9 grams and 27.4 gram Al-6.2Er master alloys are joined the graphite clay crucible, melting in crucible electrical resistance furnace, smelting temperature is 780 ℃, after treating that rafifinal and Al-6.2Er master alloy melt fully, in melt, add pure Zn113.3 gram, after stirring, add pure Mg38.6 gram again, after stirring, add 3 gram hexachloroethane (C
2Cl
6) carry out degasification, skim, at last melt is poured in the rectangle swage, cool off the demoulding after 3 minutes, the size of each ingot casting is 120 * 90 * 32 (mm
3).
The concrete food ingredient and the dosage of each element of alloy are as shown in table 1.
After the ingot casting preparation, adopt the ICP-AES method, it is inductively coupled plasma atomic emission spectrometry (used instrument is a LEEMAN SPEC-E type inductively coupled plasma atomic emission spectrometer) test ingot casting chemical ingredients, test result is as shown in table 2, and visible actual constituent is within the tolerance band of nominal composition.
Get the alloy casting state sample, produce under the NEOPHOT-21 type metaloscope in Germany and observe microtexture with polarisation.Fig. 1 (a) and Fig. 1 (b) are respectively the as-cast microstructure of Al-Zn-Mg alloy and Al-Zn-Mg-0.4Er alloy.As seen from the figure, the as-cast structure of Al-Zn-Mg alloy is thick dendrite net born of the same parents, and the dendrite of Al-Zn-Mg-0.4Er alloy basically eliminate, crystal grain is obviously refinement also.As seen the interpolation of the rare earth Er remarkable as cast condition crystal grain of refinement Al-Zn-Mg alloy really.
Ingot casting carries out hot rolling-process annealing-cold rolling (cold rolling reduction is 60%) again and makes the 2mm thin plate behind homogenizing annealing.Cold rolled sheet is made the standard tensile sample by GB GB6397-86, at 810MTS (Material Test System) cold rolling attitude of testing of materials aircraft measurements sample and quench aging attitude (+120 ℃/30h of 470 ℃/0.5h quenching timeliness) mechanical property, test result such as Fig. 2 and shown in Figure 3.Fig. 2 and Fig. 3 explanation, rare earth Er can increase substantially Al-Zn-Mg tensile strength of alloys σ
bWith yield strength σ
0.2When the nominal content of Er was 0.7%, intensity reached maximum value (the cold rolling attitude tensile strength sigma of Al-Zn-Mg-0.7Er alloy
bBe 450MPa, the aging state tensile strength sigma
bReach 513Mpa, and do not add the cold rolling attitude tensile strength sigma of Al-Zn-Mg alloy of Er
bBe 350Mpa, the aging state tensile strength sigma
bBe 420MPa), but unit elongation descends apparent in view (the cold rolling attitude unit elongation of Al-Zn-Mg alloy δ is 9%, and the cold rolling attitude unit elongation δ of Al-Zn-Mg-0.7Er alloy is 7%); When the Er addition was 0.4%, intensity and plasticity all kept higher level (Al-Zn-Mg-0.4Er alloy aging attitude tensile strength sigma
bBe 490MPa, unit elongation δ is 10%), therefore, the addition of Er is that 0.25～0.55Wt% effect is better.The abundant substructure tissue that rare earth Er mainly forms to the remarkable refining effect of crystal grain and owing to the interpolation of Er from Er the strengthening effect of Al-Zn-Mg alloy, rare earth Er can promote the timeliness of Al-Zn-Mg alloy strengthening phase to separate out in addition, increases substantially the timeliness intensity (as shown in Figure 3) of alloy.
Adopt hardness-metallographic method to determine the recrystallization temperature of alloy.Fig. 4 is Al-Zn-Mg and Al-Zn-Mg-0.4Er hardness of alloy and annealing temperature relation curve.Can tentatively determine the T of crystallization initiation temperature again of Al-Zn-Mg and Al-Zn-Mg-0.4Er alloy by Fig. 4
sAnd end of a period recrystallization temperature T
f(shown in arrow among the figure).As seen adding 0.4% Er can improve about 50 ℃ with the initial recrystallization temperature of Al-Zn-Mg alloy, and the end of a period recrystallization temperature improves about 80 ℃.Metallographicobservation analysis revealed, Al-Zn-Mg alloy recrystallize after annealing in 325 ℃, 1 hour is finished (Fig. 5 .a), and recrystallize sign (Fig. 5 .b) only appears in the Al-Zn-Mg-0.4Er alloy; The obvious alligatoring of crystal grain (Fig. 5 .c) after annealing in 450 ℃, 1 hour of Al-Zn-Mg alloy, and the Al-Zn-Mg-0.4Er alloy structure still is fine isometric crystal grains (Fig. 5 .d).As seen, the adding of Er can obviously suppress the recrystallize of Al-Zn-Mg alloy really.
Table 1 alloy nominal composition and dosage (unit: g)
Annotate: (1) each spindle batching gross weight is 1700g.(2) burn out rate: Al-3%, Mg-12%,
| Numbering | Alloy species | Pure Al | Pure Zn | Pure Mg | ??Al-6.2Er |
| ?0# | ????Al-6.0Zn-2.0Mg | ??1612.4 | ??113.3 | ??38.6 | ????0 |
| ?1# | ????Al-6.0Zn-2.0Mg-0.1Er | ??1584.9 | ??113.3 | ??38.6 | ????27.4 |
| ?2# | ????Al-6.0Zn-2.0Mg-0.25Er | ??1543.7 | ??113.3 | ??38.6 | ????68.5 |
| ?3# | ????Al-6.0Zn-2.0Mg-0.4Er | ??1502.5 | ??113.3 | ??38.6 | ????109.7 |
| ?4# | ????Al-6.0Zn-2.0Mg-0.55Er | ??1461.2 | ??113.3 | ??38.6 | ????150.8 |
| ?5# | ????Al-6.0Zn-2.0Mg-0.7Er | ??1420.1 | ??113.3 | ??38.6 | ????191.9 |
Zn-10%, master alloy Al-6.2Er does not consider scaling loss.
Each element actual constituent (g) of table 2 alloy
Claims (2)
1, a kind of Al-Zn-Mg-Er rare earth aluminium alloy, it is characterized in that: in the Al-Zn-Mg alloy, added the rare earth weight percentage and be 0.1～0.7% Er, the weight percentage of Zn is 6.0% in the described Al-Zn-Mg alloy, and the weight percentage of Mg is 2.0%, and Al is a surplus.
2, Al-Zn-Mg-Er rare earth aluminium alloy according to claim 1 is characterized in that: the addition of rare earth Er is a weight percentage 0.25～0.55%.
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|---|---|---|---|
| CN 03119119 CN1203200C (en) | 2003-03-14 | 2003-03-14 | Al-Zn-Mg-Er rare earth aluminium alloy |
| US10/747,955 US20040191111A1 (en) | 2003-03-14 | 2003-12-31 | Er strengthening aluminum alloy |
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2003
- 2003-03-14 CN CN 03119119 patent/CN1203200C/en not_active Expired - Lifetime
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