CN103789583A - Fast aging response type Al-Mg-Si-Cu-Zn series alloy and preparation method thereof - Google Patents

Fast aging response type Al-Mg-Si-Cu-Zn series alloy and preparation method thereof Download PDF

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CN103789583A
CN103789583A CN201410030681.6A CN201410030681A CN103789583A CN 103789583 A CN103789583 A CN 103789583A CN 201410030681 A CN201410030681 A CN 201410030681A CN 103789583 A CN103789583 A CN 103789583A
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alloy
novel
aging
preparation
response characteristic
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CN103789583B (en
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郭明星
庄林忠
张济山
胡晓倩
张巧霞
崔莉
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Beijing University of Technology
University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/02Alloys based on aluminium with silicon as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/06Alloys based on aluminium with magnesium as the next major constituent
    • C22C21/08Alloys based on aluminium with magnesium as the next major constituent with silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/10Alloys based on aluminium with zinc as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • C22C21/12Alloys based on aluminium with copper as the next major constituent
    • C22C21/18Alloys based on aluminium with copper as the next major constituent with zinc
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon

Abstract

The invention provides a novel Al-Mg-Si-Cu-Zn series alloy with fast aging response and a preparation method thereof. According to the invention, the novel Al-Mg-Si-Cu-Zn series alloy shows excellent fast aging response characteristic in an aging process by sufficiently utilizing the synergetic precipitation effect and synergetic strengthening effect of the main strengthening phases Mg2Si, MgZn2 and transitional phase of an Al-Mg-Si series alloy and an Al-Zn-Mg-Cu series alloy; the natural aging deterioration effect of a common Al-Mg-Si-Cu series alloy is certainly inhibited due to the simultaneous addition of Mg, Si, Cu and Zn elements and the addition of element Zn especially, the novel Al-Mg-Si-Cu-Zn series alloy has low strength and high room temperature stability after being subjected to preaging treatment at a certain temperature, which is favorable to the subsequent stamping forming of an alloy plate; a preaging-state alloy is greatly enhanced in strength after being subjected to high-temperature aging treatment and achieves the highest strength increment approaching to 150 MPa far higher than that of the traditional AA6016 and AA6111 alloys through short-term artificial aging at 185 DEG C for 20 minutes; the fast aging response characteristic is not only suitable for the preparation of an automobile outside plate, but also suitable for the related field with a special requirement on the aging precipitation speed of the alloy plate.

Description

Aging response type Al-Mg-Si-Cu-Zn is Alloy And Preparation Method fast
Technical field
The invention belongs to aluminium alloy technical field, relating to a kind of Novel Al-Mg-Si-Cu-Zn that can industrial applications is Alloy And Preparation Method, the aluminium alloy with quick aging response characteristic of being badly in need of for automotive field especially and developing, can guarantee automotive light weight technology vehicle-body outer panel aluminium alloy to high formability can and the double requirements of high bake hardening performance.
Background technology
In recent years along with the continuous quickening of automotive light weight technology process, the exploitation of aluminium alloys for automobile sheet material and correlative study also obtain greater advance, especially, because aluminium alloy is with advantages such as low density, high strength, corrosion-resistant and high forming properties, its application in automotive light weight technology process is also increased fast.Typical aluminum alloy for vehicle body plate has 2xxx, 5xxx and 6xxx to be associated gold, and wherein 6xxx is associated gold and common are AA6009, AA6010, AA6016, AA6111 and AA6022 etc.
Although can thermal treatment Al-Mg-Si to be associated golden over-all properties better, in research and application process, all find, directly after 500~570 ℃ of solution hardening processing, carry out stampingly if this is associated gold, its forming property is better.But in actual production process, major part all needs that sheet material is transported to automobile production producer and carries out follow-up stamping, the intensity that during this, sheet alloy can occur to a certain degree in natural put procedure rises, and then can reduce the forming property of sheet alloy and follow-up bake hardening performance, this phenomenon is so-called natural aging degradation effects.Therefore, automobile is as follows by the preparation technology who generally adopts in 6xxx line aluminium alloy preparation process at present: the operations such as the paint baking that alloy melting casting → homogenizing → hot rolling → cold rolling → solid solution → preageing (T4P processing) is → stamping → mopping → 170-185 ℃.The singularity of preparing due to automobile board, this just must expect that the T4P state of alloy before being shaped has lower intensity, and baking vanish process interalloy intensity can be improved significantly (being T8X state), can guarantee that like this sheet alloy has good anti-depression ability etc., therefore design of alloy and thermal treatment process exploitation are the critical paths addressing this problem.
In the past these years for how improving alloy bake hardening performance, no matter design from new alloy, as optimize Mg/Si, Cu content, or large quantity research has been carried out in the aspects such as preageing process optimization, as patent US6267922B1, US6117252, the patents such as EP1967599A1 and CN818123A, but alloy bake hardening increment is still not ideal enough, even if the bake hardening increment of commercial AA6016 and AA6111 alloy is only also 80MPa left and right.Therefore, increase substantially alloy aging response speed not only significant for the further raising of aluminium alloys for automobile bake hardening performance and the quickening of automotive light weight technology process, and also there is great importance for the exploitation of novel aluminum alloy.
Consider that reducing solute element Mg, Si, Cu and Fe content etc. can reduce T4 state alloy strength and then put forward heavy alloyed forming property, but low-alloyed bake hardening ability also can fall simultaneously in the reduction of Mg, Si and Cu element.In addition, consider MgZn 2strengthening phase can increase substantially Al-Zn-Mg-Cu and be associated golden intensity, if therefore can utilize Al-Mg-Si and Al-Zn-Mg-Cu to be associated two kinds of main strengthening phase Mg of gold simultaneously 2si and MgZn 2or its transition phase is associated golden strengthening phase as Novel Al-Mg-Si, realize the heterogeneous collaborative object of separating out and then realize heterogeneous cooperative reinforcing, the alloy of developing is bound to show very excellent quick aging response characteristic.The present invention carries out new alloy Composition Design and process exploitation according to this design philosophy.
Summary of the invention
The present invention, in order to overcome the deficiencies in the prior art, is associated golden aging response speed and the dissatisfactory feature of age hardening performance for conventional Al-Mg-Si, develops a kind of Novel Al-Mg-Si-Cu-Zn with quick aging response characteristic and is associated gold, makes full use of Mg 2si and MgZn 2thereby heterogeneous collaborative separating out with cooperative reinforcing is greatly improved alloy over-all properties.This invention alloy is particularly suitable for the automobile body outer board manufacture of aluminium alloy, has excellent bake hardening performance after making vehicle-body outer panel stamping.
The present invention is by Composition Design and optimize first and be associated golden composition range and select having the Al-Mg-Si-Cu-Zn of polyphase structure, then prepare designed alloy by operations such as melting and castings and its Precipitation behavior is studied, final definite Novel Al-Mg-Si-Cu-Zn with quick aging response is alloying constituent.Concrete preparation technology is as follows: FactSage calphad → Al-Mg-Si is alloying constituent selection → alloy preparation and melting and casting → ingot homogenization → hot rolling deformation → process annealing → cold roller and deformed → solution hardening → multistage aging processing.
The first object of the present invention is a kind of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic proposing, it is characterized in that being that the chemical composition of this alloy and mass percentage content thereof are: Zn:0.10~3.7wt%, Mg0.3~1.2wt%, Si0.3~1.2wt%, Cu0.05~0.7wt%, Fe≤0.3wt%, Mn≤0.3wt%, Cr≤0.2wt%, Ti≤0.2wt%, surplus is Al.
Preferably, the Zn of its chemical composition, Si and Cu content range are respectively: Zn0.4~3.5wt%, Si0.8~1.1wt%, Cu0.15~0.35wt%.
Preferably, the Mg/Si quality of its chemical composition Mg, Si is 0.5~1 than scope.
The second object of the present invention is to propose a kind of preparation method of above-mentioned Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic, and described preparation method comprises the following steps:
Step 1, melting and casting;
Step 2, twin-stage homogenizing;
Step 3, hot rolling deformation;
Step 4, process annealing;
Step 5, cold roller and deformed;
Step 6,540 ℃ of above solution treatment;
Step 7, Water Quenching;
Step 8, multistage aging processing.
Preferably, the twin-stage homogenizing of described step 2 is specially: the alloy sample after melting and casting is started to be warmed up to 470~485 ℃ of insulation 2~5h from room temperature with 20~40 ℃/h temperature rise rate, and then continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h, while being finally cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove again, take out.
Preferably, the hot rolling deformation of described step 3 is specially: start rolling temperature is at 545~555 ℃, hot rolling total deformation > 90%, finishing temperature >=300 ℃;
Preferably, the process annealing of described step 4 is specially, and the heat treatment furnace of the alloy sample after hot rolling deformation directly being put into 350~450 ℃ carries out the process annealing of 1~3h, then air cooling.
Preferably, the cold roller and deformed cold rolling total deformation of described step 5 is between 50%~75%, and reduction in pass is between 15%~25%.
Preferably, 540 of described step 6 ℃ of above solution treatment are specially: in salt bath furnace, carry out the solution treatment of 545~555 ℃/1-6min; The Water Quenching of described step 7 is that the alloy sample after solution treatment is directly carried out to shrend.
Preferably, the multistage aging processing of described step 8 is that the alloy sample after Water Quenching is transferred to the Pre-aging treatment that carries out 70-140 ℃/9-15h in preageing stove in 2~5min, and then places 14 days in room temperature, finally carries out 185 ℃ of artificial agings; Or the alloy sample after Water Quenching is transferred in 70-140 ℃ of preageing stove and cooled to 20~40 ℃ of taking-ups with the rate of temperature fall of 1-15 ℃/h in 2~5min, and then place 14 days in room temperature, finally carry out 185 ℃ of artificial agings.
By adopting above-mentioned technical scheme, the present invention has following superiority: Novel Al-Mg-Si-Cu-Zn of the present invention is associated gold can make full use of the interaction between each main alloy element Mg, Si, Cu and the Zn element in matrix, by suitable thermal treatment regulation and control, multiple strengthening phase being worked in coordination with separates out, in final alloy substrate, even dispersion is distributed with a large amount of different types of strengthening mutual-assistance alloys and in shorter aging time, can obtains intensity raising by a relatively large margin, realizes so-called quick aging response characteristic.Alloy of the present invention is applicable to being applied to the further development and production of the outer panel material of the more aluminium alloys for automobile of current research etc. very much.
Accompanying drawing explanation
After several novel aluminum alloy solution hardening of Fig. 1, directly carry out artificially aged changes in hardness rule.
After several novel aluminum alloy solution hardening of Fig. 2, directly carry out the changes in hardness rule of natural aging.
After several novel aluminum alloy solution hardening of Fig. 3 through natural aging the dsc analysis result after 14 days.
After several novel aluminum alloy solution hardening of Fig. 4 through natural aging after 14 days again through 185 ℃ of artificially aged changes in hardness rules.
Several novel aluminum alloys of Fig. 5 are the changes in hardness rule in Natural Aging Process after Pre-aging treatment.
Several novel aluminum alloys of Fig. 6 are the dsc analysis result after 14 days through preageing+natural aging.
Several novel aluminum alloys of Fig. 7 are through preageing+natural aging changes in hardness rule 185 ℃ of timeliness again after 14 days.
TEM microstructure when Fig. 8 T4P state 5# alloy is warmed up to 250 ℃ with 10 ℃/min.
Embodiment
Below in conjunction with specific embodiments, the present invention is further supplemented and described.
Starting material adopt respectively rafifinal, technical pure Mg, technical pure Zn, master alloy Al-20wt%Si, Al-50wt%Cu, Al-20wt%Fe, the Al-10wt%Mn etc. of 99.9wt%.Concrete fusion process in resistance furnace is, first fine aluminium is all added to crucible, furnace temperature is set in to 850 ℃, after fine aluminium fusing, adds Al-20wt%Si, Al-50wt%Cu, Al-20wt%Fe, Al-10wt%Mn master alloy, and add insulating covering agent (50wt%NaCl+50wt%KCl); Continue melt heating, treat master alloy fusing, after melt temperature reaches 750 ℃, it is stirred solute element is mixed, then after 750 ℃ of insulation 30min, set furnace temperature and make melt cool to 710 ℃, then in melt, add pure Zn and pure Mg, and fully stir it is thoroughly dissolved; Sampling analysis composition in the time that melt temperature reaches 730 ℃ again, if component metering value is lower than design load, suitably add a certain amount of master alloy according to scaling loss situation, if component metering value, higher than design load, is suitably added a certain amount of metal fine aluminium according to excessive value and diluted; Continue to skim, add after melt rises to 740 ℃ refining agent to carry out refinery by de-gassing; Then while melt temperature being down to approximately 720 ℃, add Al-5wt%Ti-1wt%B grain-refining agent and carry out agitation as appropriate, finally after this temperature insulation 10min, melt being cast in the punching block of surrounding water-cooled.Carry out an invention the specific chemical composition of alloy in table 1.
Table 1 alloy composition (mass percent, wt%) that carries out an invention
? Mg Si Cu Fe Mn Zn Cr Ti Al
1# 0.6 0.9 0.2 0.1 0.07 0 ≤0.2wt% ≤0.01wt% Surplus
2# 0.6 0.9 / 0.1 0.07 3.0 ≤0.2wt% ≤0.01wt% Surplus
3# 0.6 0.9 0.2 0.1 0.07 0.5 ≤0.2wt% ≤0.01wt% Surplus
4# 0.6 0.9 0.2 0.1 0.07 1.5 ≤0.2wt% ≤0.01wt% Surplus
5# 0.6 0.9 0.2 0.1 0.07 3.0 ≤0.2wt% ≤0.01wt% Surplus
Invention alloy cast ingot carries out homogenizing processing in recirculated air stove, treatment process is: alloy cast ingot is put into recirculated air stove, opening power, start to heat up with 20~70 ℃/h temperature rise rate, treat that temperature reaches 460~490 ℃ of insulation 1~7h, and then continue to be warmed up to 540~560 ℃ of insulation 10~25h with 20~70 ℃/h, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~70 ℃/h with stove; Then ingot casting is carried out to hot rolling deformation → process annealing → cold roller and deformed, in order to optimize better composition, part sample is directly taken from homogenizing state, a part is taken from cold rolling state, then the salt bath furnace of the block sample cutting being put into 540~560 ℃ carries out the solution treatment of 1-10min, carries out subsequently Water Quenching.Finally quenching sample is carried out to single-stage or multistage aging processing, and it is carried out to dsc analysis, microhardness and tensile property Measurement and analysis alloy and separate out the changing conditions of behavior and quick aging response.Concrete embodiment is as follows:
Embodiment 1
From carrying out an invention alloy 1#, 2# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, and then continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.And then on homogenizing block materials after treatment, directly cut sample and be placed in salt bath furnace and carry out 545~555 ℃/1-6min solution treatment (carrying out the solution treatment of 1-6min at the salt bath furnace of 545~555 ℃) and Water Quenching, directly put into subsequently the artificial aging that 185 ℃ of aging ovens carry out different time, the Precipitation behavior (in detail as shown in Figure 1) of more various alloys.
Embodiment 2
From carrying out an invention alloy 1#, 2#, 3#, 4# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h again, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.On homogenizing block materials after treatment, directly cutting subsequently sample is placed in salt bath furnace and carries out 545~555 ℃/1-6min solid solution and Water Quenching again, then directly under room temperature state, carry out natural aging, measure the Changing Pattern (in detail as shown in Figure 2) of alloy rigidity with natural aging time.In addition 14 days natural aging state samples are carried out to dsc analysis, specific embodiments is: cut out diameter 3mm × 1mm, quality is about the disk of 15mg, utilize differential scanning calorimeter Q2000(DSC) carry out differential thermal analysis, as standard specimen, be heated to 400 ℃ with the heating rate of 10 ℃/min from 20 ℃ with high-purity Al.Further grasp accordingly the Precipitation behavior difference (in detail as shown in Figure 3) of heterogeneity alloy.
Embodiment 3
From carrying out an invention alloy 1#, 2#, 3#, 4# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h again, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.On homogenizing block materials after treatment, directly cutting subsequently sample is placed in salt bath furnace and carries out 545~555 ℃/1-6min solid solution and Water Quenching again, then under room temperature state, carry out 14 days natural aging (T4 state), finally natural aging state sample is carried out the artificial aging processing of 185 ℃ of different times, measure the changes in hardness rule (in detail as shown in Figure 4) of alloy.
Embodiment 4
From carrying out an invention alloy 1#, 2#, 3#, 4# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h again, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.On homogenizing block materials after treatment, directly cutting subsequently sample is placed in salt bath furnace and carries out 545~555 ℃/1-6min solid solution and Water Quenching again, then guarantee to transfer to the Pre-aging treatment that carries out 70~140 ℃/9~15h in preageing stove in 2~5min, finally preageing state sample is carried out to natural aging under room temperature state, measure the Changing Pattern (as shown in Figure 5) of alloy rigidity with natural aging time.In addition, in order to contrast the behavior of the separating out difference of heterogeneity alloy, also carry out corresponding dsc analysis, specific embodiments is: cut out diameter 3mm × 1mm, quality is about the disk of 15mg, utilize differential scanning calorimeter Q2000(DSC) carry out differential thermal analysis, as standard specimen, be heated to 400 ℃ with the heating rate of 10 ℃/min from 20 ℃ with high-purity Al.Corresponding DSC curve as shown in Figure 6.
Embodiment 5
From carrying out an invention alloy 1#, 2#, 3#, 4# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h again, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.On homogenizing block materials after treatment, directly cutting subsequently sample is placed in salt bath furnace and carries out 545~555 ℃/1-6min solid solution and Water Quenching again, then guarantee to transfer to the Pre-aging treatment that carries out 70-140 ℃/9-15h in preageing stove in 2~5min, and preageing state sample is placed to 14 angel's alloy properties stable (being T4P (1) state) at room temperature state, finally T4P (1) state sample is carried out to the artificial aging processing of 185 ℃ of different times, measure the changes in hardness rule (in detail as shown in Figure 7) of alloy.
Embodiment 6
From carrying out an invention alloy 1#, 2#, 3#, 4# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h again, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.On homogenizing block materials after treatment, directly cutting subsequently sample is placed in salt bath furnace and carries out 545~555 ℃/1-6min solid solution and Water Quenching again, then guarantee to transfer in 2~5min in 70-140 ℃ of preageing stove and cool to 20~40 ℃ of taking-ups with the rate of temperature fall of 1-15 ℃/h, and preageing state sample is placed to 14 angel's alloy properties stable (being T4P (2) state) at room temperature state, finally T4P (2) state sample is carried out to the artificial aging processing of 185 ℃/20min, measure the hardness increment (as shown in Table 2 below) of alloy.
Embodiment 7
From carrying out an invention alloy 1# and 5# after melting and casting, it is carried out to homogenizing processing, treatment process is: start to heat up with 20~40 ℃/h temperature rise rate, treat that temperature reaches 470~485 ℃ of insulation 2~5h, continue to be warmed up to 545~555 ℃ of insulation 14~20h with 20~40 ℃/h again, and then take out sample while being cooled to 100 ℃ with the rate of temperature fall of 20~40 ℃/h with stove.After homogenizing, by ingot casting crop milling face, reheat 545~555 ℃ for hot rolling, hot rolling total deformation > 90%, finishing temperature >=300 ℃, hot rolling finish to gauge thickness is 4.0mm; Sheet material after hot rolling is carried out to the anneal of 350-450 ℃/1-3h, be then cold rolled to 1mm thick, reduction in pass is in 15~25%, and total deformation is 75%; Sheet material after cold rolling is carried out to 545~555 ℃/1-6min solid solution and Water Quenching, then guarantee to transfer in 2~5min in 70-140 ℃ of preageing stove and cool to 20~40 ℃ of taking-ups with the rate of temperature fall of 1-15 ℃/h, and preageing state sample is placed to 14 angel's alloy properties stable (being T4P (2) state) at room temperature state, finally T4P (2) state sample is carried out to the artificial aging processing of 185 ℃/20min, measure respectively the tensile property (as shown in Table 3 below) of T4P (2) state and high temperature artificial aging state alloy.
Table 2 different states alloy hardness increment after 185 ℃ of 20min ageing treatment
Table 3 sheet alloy T4P (2) state and high temperature artificial aging state mechanical property
Because being all associated golden Precipitation behavior to Al-Mg-Si, alloying constituent, microstructure and heat treating regime have impact, separate out the impact of behavior in order to eliminate the Deformation structure's alloy forming in hot-work and cold working process, thereby guarantee that Novel Al-Mg-Si-Cu-Zn that optimization better has a quick aging response is alloying constituent, different heat treatment state alloy used is all taken from homogenizing ingot casting sample after treatment.The Al-Mg-Si-Cu-Zn of embodiment 1-6 after different heat treatment art breading is associated golden changes in hardness and corresponding DSC curve as shown in Fig. 1-7.As seen from Figure 1, with respect to the 1# alloy that does not contain Zn, no matter still do not contain the 5# alloy of Cu containing the 2# alloy of Cu, after solution hardening, directly carry out the artificial aging of 185 ℃ of different times, its timeliness speed of separating out is all faster than containing the 1# alloy of Zn, and peak hardness is also all higher than 1# alloy.As seen from Figure 2, no matter be not still associated gold containing the Al-Mg-Si of Zn containing Zn, the hardness rising that as-quenched temper sample all can occur to a certain degree in room temperature put procedure finally tends towards stability, but rises less containing the 4# alloy of 1.5wt%Zn.Several exemplary alloy are carried out to corresponding dsc analysis can obviously be found out, the Al-Mg-Si-Cu-Zn that adds a certain amount of Zn is associated that golden low temperature is separated out peak and considerable change all occurs at back dissolving peak, particularly in the time that Zn content adds 3.0wt% to, peak temperature is the β of 250 ℃ " separates out mutually significantly reach occurs; even if the alloy after natural aging treatment is described, " separating out of phase has certain promoter action to add a certain amount of element Zn also to main strengthening phase-β.According to embodiment 3, if several natural aging state alloys are carried out to the processing of corresponding 185 ℃ of high temperature artificial agings again, as seen from Figure 4, Al-Mg-Si-Cu after interpolation element Zn is associated golden high-temperature aging speed of separating out obviously to be accelerated, but along with the variation of Zn content, Precipitation speed difference is larger, due to this exerts an influence to its interaction mainly due to each main alloying element content.Can accelerate T4 state alloy high-temp Precipitation speed although add a certain amount of element Zn, this speed of separating out is still not ideal enough.If invention alloy is carried out to corresponding Pre-aging treatment (embodiment 4), several alloys are comparatively stable at room temperature put procedure performance, seemingly all there will not be the hardness rise phenomenon (as shown in Figure 5) of as-quenched temper alloy in Natural Aging Process with the 1# alloy type that does not contain Zn, and T4P state sample is carried out to dsc analysis and can find, low temperature is separated out peak and is all disappeared, after adding element Zn, peak temperature is the β of 250 ℃, and " separating out mutually same generation the in peak significantly moves forward.Carry out high temperature artificial aging (embodiment 5) if preageing state alloy is added again to the sample of natural aging placement in 14 days, as seen from Figure 7, after alloy interpolation element Zn, high-temperature aging speed of separating out all has largely increases, particularly 2#, 3# and 5# alloy, and observe containing Zn alloy and be easy to separate out a large amount of spherical precipitation phases (as shown in Figure 8) under transmission electron microscope.
In addition, consider that the Novel Al-Mg-Si-Cu-Zn with quick aging response characteristic is associated the manufacture that gold is applicable to being applied to body of a motor car outside plate alloy more, therefore, can further contrast several alloy T4 states and the T4P state hardness increment (as shown in table 2) at 185 ℃ of timeliness 20min.Can be found out by table, the 1# alloy of T4 state is because natural aging degradation effects is serious, and it even occurs hardness decline phenomenon after 185 ℃/20min timeliness, but after adding element Zn, this phenomenon can thoroughly be avoided.In addition, add element Zn several alloys afterwards, except 4# alloy, other several T4P state alloys carry out hardness increment after 185 ℃ of 20min timeliness all higher than the hardness increment of T4P state 1# alloy, particularly adopt embodiment 6 sample after treatment, this further illustrates Novel Al-Mg-Si-Cu-Zn and is associated gold several strengthening phases in matrix after suitable thermal treatment process is processed and can realizes and collaboratively preferably separate out and strengthen fast matrix.According to the above results, select again alloy part (1# and 5#) to carry out the further contrast of embodiment 7, can find the in short-term artificial aging processing of 5# alloy through 185 ℃/20min by table 3, its yield strength increment 150MPa nearly, this increment is far above the increment of the conventional AA6016 of automobile exterior panel and AA6111 alloy 80MPa left and right.
In sum, the present invention is by Composition Design and processing and heat treatment process optimization, Novel Al-Mg-Si-Cu-Zn is associated to the interaction between each main alloying element Mg, Si, Cu and Zn in gold and has carried out regulation and control well, make this be associated the more conventional Al-Mg-Si of gold and be associated gold utensil and have more excellent quick aging response characteristic.In addition, preparation technology newly developed not only can make alloy aging response speed accelerate, and is associated golden natural aging degradation effects but also can suppress as-quenched temper Al-Mg-Si, makes sheet alloy have excellent forming property and bake hardening performance.Therefore, this invention alloy and technique are not only applicable to being applied to the manufacture of automotive light weight technology vehicle-body outer panel aluminium alloy very much, and also there is certain directive significance for other field with exploitation, processing and the application of the novel aluminum alloy of quick aging response, be worth automobile production producer and aluminium alloy enterprise to be paid attention to this invention alloy and relevant preparation technology, make it can be promoted and apply in this field as early as possible.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is by claims and be equal to and limit.

Claims (10)

1. one kind has Novel Al-Mg-Si-Cu-Zn series alloys of quick aging response characteristic, it is characterized in that being that the chemical composition of this alloy and mass percentage content thereof are: Zn:0.10~3.7wt%, Mg 0.3~1.2wt%, Si 0.3~1.2wt%, Cu 0.05~0.7wt%, Fe≤0.3wt%, Mn≤0.3wt%, Cr≤0.2wt%, Ti≤0.2wt%, surplus is Al.
2. Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic according to claim 1, it is characterized in that: Zn, Si and the Cu content range of its chemical composition are respectively: Zn0.4~3.5wt%, Si 0.8~1.1wt%, Cu 0.15~0.35wt%.
3. Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic according to claim 1, is characterized in that: the Mg/Si quality of its chemical composition Mg, Si is 0.5~1 than scope.
4. according to the preparation method of the Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic described in claim 1-3 any one, described preparation method comprises the following steps:
Step 1, melting and casting;
Step 2, twin-stage homogenizing;
Step 3, hot rolling deformation;
Step 4, process annealing;
Step 5, cold roller and deformed;
Step 6,540 ℃ of above solution treatment;
Step 7, Water Quenching;
Step 8, multistage aging processing.
5. the preparation method of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic as claimed in claim 3, it is characterized in that: the twin-stage homogenizing of described step 2 is specially: the alloy sample after melting and casting is started to be warmed up to 470 ~ 485 ℃ of insulation 2 ~ 5h from room temperature with 20 ~ 40 ℃/h temperature rise rate, and then continue to be warmed up to 545 ~ 555 ℃ of insulation 14 ~ 20h with 20 ~ 40 ℃/h, while being finally cooled to 100 ℃ with the rate of temperature fall of 20 ~ 40 ℃/h with stove again, take out.
6. the preparation method of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic as claimed in claim 4, it is characterized in that: the hot rolling deformation of described step 3 is specially: start rolling temperature is at 545 ~ 555 ℃, hot rolling total deformation > 90%, finishing temperature >=300 ℃.
7. the preparation method of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic as claimed in claim 4, it is characterized in that: the process annealing of described step 4 is specially, the heat treatment furnace that alloy sample after hot rolling deformation is directly put into 350 ~ 450 ℃ carries out the process annealing of 1 ~ 3h, then air cooling.
8. the preparation method of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic as claimed in claim 4, it is characterized in that: the cold roller and deformed cold rolling total deformation of described step 5 is between 50% ~ 75%, and reduction in pass is between 15% ~ 25%.
9. the preparation method of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic as claimed in claim 4, is characterized in that: 540 ℃ of above solution treatment of described step 6 are specially: in salt bath furnace, carry out the solution treatment of 545 ~ 555 ℃/1-6min; The Water Quenching of described step 7 is that the alloy sample after solution treatment is directly carried out to shrend.
10. the preparation method of Novel Al-Mg-Si-Cu-Zn series alloys with quick aging response characteristic as claimed in claim 4, it is characterized in that: the multistage aging processing of described step 8 is that the alloy sample after Water Quenching is transferred to the Pre-aging treatment that carries out 70-140 ℃/9-15h in preageing stove in 2 ~ 5min, and then place 14 days in room temperature, finally carry out 185 ℃ of artificial agings; Or the alloy sample after Water Quenching is transferred in 70-140 ℃ of preageing stove and cooled to 20 ~ 40 ℃ of taking-ups with the rate of temperature fall of 1-15 ℃/h in 2 ~ 5min, and then place 14 days in room temperature, finally carry out 185 ℃ of artificial agings.
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