CN101353743A - Niobium and ytterbium-containing anti-recrystallizing corrosion resistant aluminum alloy - Google Patents

Niobium and ytterbium-containing anti-recrystallizing corrosion resistant aluminum alloy Download PDF

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CN101353743A
CN101353743A CNA2007100354345A CN200710035434A CN101353743A CN 101353743 A CN101353743 A CN 101353743A CN A2007100354345 A CNA2007100354345 A CN A2007100354345A CN 200710035434 A CN200710035434 A CN 200710035434A CN 101353743 A CN101353743 A CN 101353743A
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陈康华
张茁
方华婵
祝昌军
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Central South University
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Abstract

The invention discloses a re-crystalization resistant corrosion resistant aluminium alloy, which consists of major alloying elements Al-Mg-(Zn-Cu) and Zr-Cr-Nb-Yb accounting for 0.1 to 1.2 percent of the mass percent of the alloy. The Al-Mg-(Zn-Cu) alloy is added with Zr, Cr, Nb and Yb to form a multielement aluminide dispersed phase, thus effectively restraining the re-crystalization of the Al-Mg-(Zn-Cu) alloy, maintaining the deformation recovery organization and improving the strength, fracture tenacity and stress corrosion resistance of the alloy; furthermore, the prices of Zr, Cr, Nb and Yb are relatively inexpensive, therefore the aluminium alloy is applicable to industrialized production.

Description

Contain niobium and ytterbium anti-recrystallizing corrosion resistant aluminum alloy
Technical field
The invention belongs to the metal alloy field, particularly anti-recrystallizing corrosion resistant aluminum alloy.
Background technology
The alloying of aluminium and microalloying are the basic means of improving all kinds of aluminium alloy capabilities and development of new aluminium alloy.Forming fine disperse phase by multicomponent microalloying, suppress recrystallize and grain growth, maintenance deformation-recovery tissue effectively, is one of approach that improves simultaneously intensity of aluminum alloy and corrosion resistance.In recent years, Zr is used widely in the aluminium alloy microalloying, and Zr adds in the aluminium alloy, forms metastable L1 2Type and Al Al matrix coherence 3Zr disperse phase has improved the recrystallize drag of alloy, has improved stress corrosion performance, but metastable L1 2Type Al 3When growing at high temperature, Zr can change stable DO in homogenizing and the solution treatment into the non-coherence of Al matrix 23Type Al 3Zr disperse phase, the effect that suppresses recrystallize can decrease.Add micro alloying element Sc and suppress recrystallize effect best bet at present, it can form the fine Al with the matrix coherence 3Sc disperse phase particle can improve the toughness and the anti-stress corrosion performance of alloy when improving intensity; Sc, Zr join in the aluminium alloy simultaneously, play the effect that improves intensity and stress corrosion resistance equally.But, because costing an arm and a leg of Sc is not suitable for actual industrial production.
Summary of the invention
The objective of the invention is the low-cost micro alloying element of compound interpolation in Al-Mg-(Zn-Cu) aluminium alloy, to form new and effective polynary aluminide disperse phase, the recrystallize that effectively suppresses alloy, intensity, anti-fracture toughness property and the anti-stress corrosion performance of raising alloy.
Detailed technology scheme of the present invention is: a kind of anti-recrystallizing corrosion resistant aluminum alloy, comprise main alloying element Al-Zn-Mg or Al-Zn-Mg-Cu or Al-Mg or Al-Cu-Mg, and total content to account for alloy mass per-cent be 0.1～1.2% Zr-Cr-Nb-Yb.Wherein Zn, Mg, Cu account for the mass percent of alloy and are: Zn:0～9.2%; Mg:0.2～5.6%; Cu:0～6.8%.
Wherein Zr, Cr, Nb and the Yb mass percent that accounts for alloy preferably is respectively: Zr:0.05～0.2%; Cr:0.05～0.3%; Nb:0.04～0.1; Yb:0.05～0.4%.
In above-mentioned aluminium alloy, also can add Mn, Ti by trace, the mass percent that adds Mn, Ti is: Mn:0～0.5%; Ti:0～0.1%.
The present invention adds in the Zr in Al-Mg-(Zn-Cu) alloy, compound interpolation Cr, Nb and rare earth element y b, form polynary disperse phase, the recrystallize that has effectively suppressed Al-Mg-(Zn-Cu) alloy, keep the deformation recovery tissue, improved intensity, fracture toughness property and the anti-stress corrosion performance of Al-Zn-Mg-Cu or Al-Zn-Mg alloy.And Zr, Cr, Nb and rare earth metal y b price are relatively cheap, are suitable for suitability for industrialized production.Anti-recrystallizing corrosion resistant Al-Mg-(Zn-Cu) alloy that contains Zr, Cr, Nb and rare earth element y b of the present invention may be used on every field.
Description of drawings
Fig. 1: the A-1 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 1;
Fig. 2: the A-2 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 2;
Fig. 3: the A-3 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 3;
Fig. 4: the A-4 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 4;
Fig. 5: the A-5 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 5;
Fig. 6: the A-6 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 6;
Fig. 7: the A-7 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 7;
Fig. 8: the A-8 alloy solid solution attitude metallographic microstructure figure of Comparative Examples 8;
The B-1 alloy solid solution attitude metallographic microstructure figure of Fig. 9: embodiment 1;
The B-2 alloy solid solution attitude metallographic microstructure figure of Figure 10: embodiment 2;
The B-3 alloy solid solution attitude metallographic microstructure figure of Figure 11: embodiment 3;
The B-4 alloy solid solution attitude metallographic microstructure figure of Figure 12: embodiment 4;
The B-5 alloy solid solution attitude metallographic microstructure figure of Figure 13: embodiment 5;
The B-6 alloy solid solution attitude metallographic microstructure figure of Figure 14: embodiment 6;
The B-7 alloy solid solution attitude metallographic microstructure figure of Figure 15: embodiment 7;
Figure 16: the alloy crack growth rate v-stress intensity factor graphic representation of Comparative Examples 1, embodiment 1 in the 3.5%NaCl aqueous solution under the T6 aging state;
Figure 17: the alloy crack growth rate v-stress intensity factor graphic representation of Comparative Examples 2, embodiment 2 in the 3.5%NaCl aqueous solution under the T6 aging state;
Figure 18: the alloy crack growth rate v-stress intensity factor graphic representation of Comparative Examples 3, embodiment 3 in the 3.5%NaCl aqueous solution under the T6 aging state;
Figure 19: the alloy crack growth rate v-stress intensity factor graphic representation of Comparative Examples 4, embodiment 3 in the 3.5%NaCl aqueous solution under the T6 aging state;
Figure 20: the alloy crack growth rate v-stress intensity factor graphic representation of Comparative Examples 5, embodiment 4 in the 3.5%NaCl aqueous solution under the T6 aging state;
Figure 21: the alloy crack growth rate v-stress intensity factor graphic representation of Comparative Examples 9, embodiment 2 in the 3.5%NaCl aqueous solution under the T6 aging state.
Embodiment
Comparative Examples 1: the ingot metallurgy legal system is equipped with the A-1 alloy in the table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Zr master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 2: the A-2 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Zr, Al-Cr master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 3: the A-3 alloy in the preparation table 1.The preparation method is as described in the Comparative Examples 1.
Comparative Examples 4: the A-4 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Zr, Al-Sc master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 5: the A-5 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add the Al-Zr master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 6: the A-6 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add the Al-Cu master alloy, reduce to 760 ℃, add technical pure Mg (purity is 99.9%), after removing surperficial slag, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 7: the A-7 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 760 ℃, after the rafifinal fusing, add technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 8: the A-8 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Zr, Al-Cr, Al-Mn, Al-Ti master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Comparative Examples 9: the A-9 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Cr, Al-Zr, Al-Yb master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 1: B-1 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Cr, Al-Zr, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 2: B-2 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Cr, Al-Zr, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 3: B-3 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Cr, Al-Zr, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 4: B-4 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cr, Al-Zr, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 5: B-5 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Cr, Al-Zr, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Mg (purity is 99.9%), after removing surperficial slag, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 6: B-6 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cr, Al-Zr, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Mg (purity is 99.9%), after removing surperficial slag, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
Embodiment 7: B-7 alloy in the preparation table 1.Rafifinal (purity is 99.99%) is joined the graphite clay crucible, melting in electrical crucible, smelting temperature is 780 ℃, after the rafifinal fusing, add Al-Cu, Al-Zr, Al-Cr, Al-Mn, Al-Ti, Al-Nb, Al-Yb master alloy, reduce to 760 ℃, add technical pure Zn (purity is 99.9%), fusing also stirs the back and adds technical pure Mg (purity is 99.9%), remove surperficial slag after, add 0.2%～0.4% hexachloroethane (C 2Cl 6) degasification of refining agent deslagging, left standstill 10～15 minutes, pour in the swage cooling back demoulding.
A-1 alloy, A-2 alloy, A-3 alloy, A-4 alloy, B-1 alloy, B-2 alloy, B-3 alloy cast ingot are behind 465 ℃/24h homogenizing annealing, carry out hot extrusion at 410 ℃～430 ℃ again, extrusion ratio is 12.2, carry out solution treatment afterwards, the solid solution system is as follows: 450 ℃ are incubated 1 hour, are warming up to 470 ℃ of insulations 1 hour, continue to be warming up to 480 ℃ of insulations 2 hours, cold-water quench, T6 timeliness (130 ℃ are incubated 24 hours).
A-5 alloy, B-4 alloy, A-8 alloy, B-7 alloy cast ingot carry out hot extrusion at 410 ℃-430 ℃ again behind 465 ℃/24h homogenizing annealing, extrusion ratio is 12.2, carry out solution treatment afterwards, solid solubility temperature is 475 ℃, cold-water quench, T6 timeliness (120 ℃ are incubated 24 hours).
A-6 alloy, B-5 alloy cast ingot are behind 500 ℃/20h homogenizing annealing, carry out hot extrusion at 410 ℃～430 ℃ again, extrusion ratio is 12.2, carry out solution treatment afterwards, the solid solution system is as follows: 490 ℃ are incubated 2 hours, be warming up to 506 ℃ of insulations 20 minutes, cold-water quench, T6 timeliness (160 ℃ are incubated 18 hours).
A-7 alloy, B-6 alloy cast ingot carry out hot extrusion at 410 ℃～430 ℃ again behind 470 ℃/13h homogenizing annealing, extrusion ratio is 12.2, carry out solution treatment afterwards, the solid solution system is as follows: 450 ℃ are incubated 1 hour, are warming up to 470 ℃ of insulations 1 hour, continue to be warming up to 480 ℃ of insulations 1 hour.
Get alloy solid solution attitude sample, under the MeF3A metaloscope, observe microtexture behind electropolishing and the anode overlay film with polarized light.Fig. 1～8 are respectively the solid solution attitude micro-organization chart of A-1～A-8 alloy; Fig. 9～Figure 15 is respectively the solid solution attitude micro-organization chart of B-1～B-7 alloy.
Recrystallize has wholly or in part taken place in the A-1～A-8 of Comparative Examples (corresponding to accompanying drawing 1～8) alloy after extruding, solution treatment.And the solid solution attitude microstructure of the B-1 of compound interpolation Zr-Cr-N-Yb～B-7 alloy (corresponding to accompanying drawing 9～15) is fibrous processing attitude tissue, and recrystallize does not take place.
In Al-Zn-Mg-Cu or Al-Zn-Mg alloy, tangible recrystallize (corresponding to accompanying drawing 1,3,5,2) has taken place in the A-2 alloy that adds A-1, A-3, A-5 alloy and the interpolation Zr-Cr of micro-Zr separately, and the B-1 of compound interpolation Zr-Cr-Nb-Yb, B-2, B-3, B-4 still keep fibrous processing attitude tissue (corresponding to accompanying drawing 9～12) substantially, with the A-8 alloy ratio that the part recrystallize takes place (referring to accompanying drawing 8), the B-7 alloy of compound interpolation Zr-Cr-Nb-Yb still keeps fibrous processing attitude tissue (referring to accompanying drawing 15) substantially.Therefore say that compound interpolation Zr-Cr-Nb-Yb has suppressed recrystallize preferably in Al-Zn-Mg-Cu or the Al-Zn-Mg alloy.
In Al-Cu-Mg and Al-Mg alloy, A-6, the A-7 alloy that does not add Zr-Cr-Nb-Yb takes place significantly, and (fully) recrystallize also is fine isometric crystal grains (corresponding to accompanying drawing 6,7), and the B-5 of compound interpolation Zr-Cr-Nb-Yb, B-6 alloy still keep fibrous processing attitude tissue (corresponding to accompanying drawing 13,14) substantially, therefore say that compound interpolation Zr-Cr-Nb-Yb has suppressed recrystallize preferably in Al-Cu-Mg or the Al-Mg alloy.
Table 2 is under the T6 state, mechanical performance data tables such as microalloying Al-Zn-Mg-Cu or Al-Zn-Mg hardness of alloy, stress intensity.As can be seen from Table 2, the hardness of the B-1 alloy aging attitude of interpolation Zr-Cr-Nb-Yb and stress corrosion performance all are better than the A-1 alloy in the Comparative Examples 1; The hardness of the B-2 alloy aging attitude of interpolation Zr-Cr-Nb-Yb and stress corrosion performance all are better than the A-2 alloy in the Comparative Examples 2 and add the A-9 alloy of Zr-Cr-Yb; The hardness of the B-3 alloy aging attitude of interpolation Zr-Cr-Nb-Yb and stress corrosion performance all are better than Comparative Examples 3 and add the A-3 alloy of Zr and the A-4 alloy that Comparative Examples 4 is added Zr-Sc; The hardness of the B-4 alloy aging attitude of interpolation Zr-Cr-Nb-Yb and stress corrosion performance all are better than the A-5 alloy in the Comparative Examples 5.The hardness of the B-7 alloy aging attitude of interpolation Zr-Cr-Nb-Yb and stress corrosion performance all are better than the A-8 alloy in the Comparative Examples 8.
The B-1 alloy stress corrosive nature of adding Zr-Cr-Nb-Yb is better than the A-1 alloy (referring to accompanying drawing 16) that Comparative Examples 1 only contains Zr; The B-2 alloy stress corrosive nature of adding Zr-Cr-Nb-Yb is better than the A-2 alloy (referring to accompanying drawing 17) that Comparative Examples 2 contains Zr-Cr, is better than containing the A-9 alloy (referring to accompanying drawing 21) of Zr-Cr-Yb simultaneously; The B-3 alloy stress corrosive nature of adding Zr-Cr-Nb-Yb is better than the A-3 alloy (referring to accompanying drawing 18) that Comparative Examples 3 only contains Zr; The B-3 alloy stress corrosive nature of adding Zr-Cr-Nb-Yb all is better than the A-4 alloy (referring to accompanying drawing 19) that Comparative Examples 4 contains Zr-Sc; The B-4 alloy stress corrosive nature of adding Zr-Cr-Nb-Yb is better than the A-5 alloy (referring to accompanying drawing 20) that Comparative Examples 5 contains Zr.Intensity, plasticity and anti-fracture toughness property that Zr-Cr-Nb-Yb has not only improved Al-Zn-Mg-(Cu) alloy are added in more than explanation, have also improved the anti-stress corrosion performance of alloy simultaneously.
Alloying constituent in each application examples of table 1 (mass percent, %)
Figure A20071003543400091
Microalloying Al-Zn-Mg-(Cu) hardness of alloy, mechanical property and stress intensity factor under the table 2T6 aging state
Figure A20071003543400102
Annotate: K ICDirection of crack propagation is the direction of extrusion during test

Claims (3)

1. one kind contains niobium and ytterbium anti-recrystallizing corrosion resistant aluminum alloy, comprise main alloying element Al-Zn-Mg-Cu or Al-Zn-Mg or Al-Mg or Al-Mg-Cu, it is characterized in that: comprise also that to account for alloy mass per-cent be 0.1～1.2% Zr-Cr-Nb-Yb, the mass percent that described Zn, Mg, Cu element account for alloy is respectively: Zn:0～9.2%; Mg:0.2～5.6%; Cu:0～6.8%.
2. aluminium alloy as claimed in claim 1 is characterized in that: the mass percent that described Zr, Cr, Nb and Yb account for alloy is respectively: Zr:0.05～0.2%; Cr:0.05～0.3%; Nb:0.04～0.1%; Yb:0.05～0.4%.
3. aluminium alloy as claimed in claim 1 or 2 is characterized in that: described aluminium alloy also comprises Mn, Ti, and the mass percent that described Mn, Ti account for alloy is: Mn:0～0.5%; Ti:0～0.1%.
CNA2007100354345A 2007-07-25 2007-07-25 Niobium and ytterbium-containing anti-recrystallizing corrosion resistant aluminum alloy Pending CN101353743A (en)

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