CN109666812A - A kind of high thermal stability ultra-high-strength aluminum alloy and preparation method thereof - Google Patents
A kind of high thermal stability ultra-high-strength aluminum alloy and preparation method thereof Download PDFInfo
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- CN109666812A CN109666812A CN201910124137.0A CN201910124137A CN109666812A CN 109666812 A CN109666812 A CN 109666812A CN 201910124137 A CN201910124137 A CN 201910124137A CN 109666812 A CN109666812 A CN 109666812A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
- C22F1/053—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with zinc as the next major constituent
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Abstract
The invention discloses a kind of high thermal stability ultra-high-strength aluminum alloys and preparation method thereof, belong to aluminum alloy processing technology field, this novel alloy ingredient proposed by the invention has novelty, by calculating a kind of preferred stabilizing element Co, the interface of main hardening constituent can preferentially be segregated to, its interface energy is reduced, inhibits the dynamic process of its roughening of growing up, to effectively improve the thermal stability of alloy property.The advantage of the ingredient design of this innovation is, does not need to design new precipitated phase, the content of other alloying elements and common 7 is alloy without significant difference；This novel alloy provided by the present invention is due to introducing new stabilizing element Co, heat treatment process window can be relaxed, this has benefited from the segregation of Co, improve the thermal stability of main precipitation strength η ' phase in alloy, peak timeliness intensity can maintain 50 hours or more, significantly larger than other 7 line aluminium alloys at 150 DEG C in alloy of the present invention.
Description
Technical field
The invention belongs to aluminum alloy processing technology fields, and in particular to a kind of high thermal stability ultra-high-strength aluminum alloy and its system
Preparation Method.
Background technique
Aluminium alloy relies primarily on the dispersion-strengtherning of precipitated phase, and the thermal stability of main precipitation strength phase is generally insufficient,
100~150 DEG C or more will grow up rapidly and intensity of aluminum alloy is caused to decline rapidly.Ultra-high-strength aluminum alloy refers to intensity 650MPa
Above aluminium alloy has outstanding advantages of density is small, specific strength is high, processing performance is good and corrosion-resistant.As China's aviation is navigated
It, the fast development in the fields such as energy traffic and national defense industry, high-strength and heat-resisting aluminium alloy demand is continuously increased.At present
Casting heat-resistant aluminum alloy is mainly Al-Cu and Al-Si alloy, but (Al-Cu intensity is generally below 400MPa, Al- to intensity deficiency
Si intensity is lower than 300MPa).Deformation thermostable aluminum alloy chooses the different addition element such as Si, Mg, Cu, Zr, Ni, Mn, Ti, Fe,
The high new precipitated phase of thermal stability is formed, inhibits Recovery and recrystallization process, to improve the softening resistant to high temperatures of alloy and resist compacted
It is denaturalized energy.But this kind of heat-resisting precipitated phase stock size is larger, mostly non-coherence phase, and invigoration effect is limited, it is also difficult to realize
The high intensity of 650MPa or more.Ultra-high-strength aluminum alloy is typically based on 7 line aluminium alloys (Al-Zn-Mg-Cu) exploitation, by continuous
Its alloying element content (total content is more than 12~15%) Lai Tigao precipitation strength efficiency is improved, maximum intensity is reachable at present
800MPa or more, but since main phases precipitated η ' phase thermal stability is poor, service temperature is more than 100 DEG C and grows up and change rapidly
For η phase, intensity sharply declines, and loses the service ability of its superhigh intensity.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of high thermal stability ultra-high-strength aluminum alloy and its
Preparation method.
To achieve the goals above, the invention adopts the following technical scheme:
The present invention provides a kind of high thermal stability ultra-high-strength aluminum alloy, and be made of by weight percentage following components: Zn contains
It is 1.8~3%, Cu content be 0.3~2%, Co content be 0.2~2.0%, Zr content is 0.1 that amount, which is 8~14%, Mg content,
~0.3%, impurity element S i content≤0.08%, Impurity Fe≤0.1%, remaining content of impurities≤0.1%, remaining is
Aluminium.
The inventive concept total as one, the present invention also provides the preparation sides of the high thermal stability ultra-high-strength aluminum alloy
Method, comprising the following steps:
(1) it stocks up: carrying out ingredient according to the design component of alloy, prepare melting；
Wherein Al, Zn, Mg, Cu, Co are pure metal, and Al-Zr is intermediate alloy；
(2) founding: smelting temperature is 740~760 DEG C, addition Al, Zn, Cu and Al-Zr intermediate alloy, standing of skimming,
Mg, Co are added under set temperature into melt, is cast after standing, casting is taken out after solidifying completely；
(3) it homogenizing: carrying out Homogenization Treatments in Muffle furnace, homogenization temperature is 460 ± 50 DEG C, the time is 24~
36h；
(4) thermal deformation: heat distortion temperature is 450 ± 50 DEG C, cumulative deformation > 70%；
(5) solution treatment: alloy after thermal deformation carries out solution treatment, and solution annealing temperature is 480 ± 50 DEG C, and the time is
2~4h then carries out water quenching；
(6) ageing treatment: the alloy after solid solution is heated at 120~150 DEG C, carries out ageing treatment.
Preferably, in step (1), the pure metal and Al-Zr intermediate alloy are preheated, preheating temperature be 120~
150 DEG C, preheating time is 1~2h.
Preferably, founding in the step (2), specifically:
A) control smelting temperature is 740~760 DEG C, will be closed among corresponding pure Al, Zn, Cu metal charge and Al-Zr
Gold is melted under the conditions of 760 DEG C, and electromechanical stirring then passes through the processing of chlorine hydrogen gaseous mixture refining techniques and melt filtration；
B) Mg and Co pieces are added in 730 DEG C of temperature ranges to filtered melt, be sufficiently stirred after fusing, filter and
Chlorine hydrogen gaseous mixture refining treatment, sufficient standing 25min or more after refining；
C) when temperature is down to 720 DEG C, the alloy melt after sufficient standing is directly poured, is continuously or semi-continuously cast
It makes.
Preferably, in step (6), institution of prescription is that 12~50h is kept the temperature at 150 DEG C.
The principle of the present invention: the present invention is that main precipitation strength phase η ' is mutually easy roughening in ultra-high-strength aluminum alloy for 7
Feature, according to first principle energetics calculated result, as shown in Figure 1, selecting Co element as stabilizing element, by inclined
Analysis is wrapped near precipitated phase, is reduced its interface energy in aluminum substrate, the further diffusion of solute is hindered, to inhibit η ' phase
Roughening of growing up, can effectively delay alloy overaging, improve thermostabilization and the anti-stress corrosiveness of alloy.
The present invention is to provide a kind of novel ultra-high-strength aluminum alloy ingredient and preparation method, which can be using conventional molten
Casting method preparation, and superhigh intensity, good anti-stress corrosion performance and thermal stability can be had both.Experiment shows in Zn+Mg
The 7 of+Cu total content~12% are to add only 0.5% Co, tensile strength is basically unchanged (650MPa), at 150 DEG C in alloy
Lower timeliness 84 hours, alloy strength still are able to maintenance~600MPa high intensity, calculate with the 92% of peak strength, thermal stability
Improve 60%.It is to add 1.0% Co in alloy the 7 of Zn+Mg+Cu total content~15%, tensile strength can be promoted to
750MPa or more, thermal stability then improve 100%, i.e., timeliness 108 hours at 150 DEG C, and alloy strength still is able to maintain~
The superhigh intensity (the 92% of peak strength) of 700MPa, and Grain Boundary Precipitates are discontinuous, anti-stress corrosion performance is good.
Compared with prior art, advantageous effects of the invention are as follows:
(1) this novel high thermal stability ultrahigh-strength aluminum alloy material proposed by the invention, preparation flow and other
High-strength 7 be that alloy is essentially identical, without increasing any new process, does not also increase technical difficulty and production cost.
(2) this novel alloy ingredient proposed by the invention has novelty, by calculating a kind of preferred stabilisation
Elements C o can preferentially segregate to the interface of main hardening constituent (η ' phase), reduce its interface energy, inhibit the power of its roughening of growing up
Process, to effectively improve the thermal stability of alloy property.The advantage of the ingredient design of this innovation is, does not need to design
New precipitated phase, the content of other alloying elements and common 7 is alloy without significant difference.
(3) this novel alloy provided by the present invention can relax hot place due to introducing new stabilizing element Co
Process window is managed, this has benefited from the segregation of Co, improves the thermal stability of main precipitation strength η ' phase in alloy, alloy of the present invention
In at 150 DEG C peak timeliness intensity can maintain 50 hours or more, significantly larger than other 7 line aluminium alloys.
(4) this novel alloy provided by the present invention can take into account high-intensitive and anti-stress corrosion performance.For common
7 be alloy, often through different degrees of Wetted constructures, sacrifices intensity to improve alloy anti-stress corrosion performance, the present invention
Crystal boundary and crystalline substance due to improving the thermal stability of precipitation strength η ' phase in alloy, with the extension of aging time, inside alloy
The reinforcing η ' of interior precipitation mutually can keep dispersed and tiny, to realize that good anti-stress corrosion performance and superelevation are strong simultaneously
Degree.
Detailed description of the invention
Fig. 1 first principle energetics calculates prediction Co element and segregates to η ' strongly mutually and stablize its interface.
Fig. 2 is the microstructure of 1 alloy of comparative example (no Co) 150 DEG C of timeliness: (a) timeliness 6h；(b) timeliness 50h.
Fig. 3 is the microstructure of 2 alloy of present example (containing 1.0%Co) through 150 DEG C of timeliness 50h.
Specific embodiment
Below in conjunction with example, the present invention is described further, provides specific embodiment and operating process, but this
The embodiment of invention is without being limited thereto.
Comparative example 1 (the reference alloy of no Co addition)
One, alloying component matches
Two, alloy melting
Fine aluminium is melted at 740 DEG C first, Zn, Cu pure element and Al-Zr intermediate alloy is then added, is all melted to it
Afterwards, it skims standing, then melt temperature is controlled at 730 DEG C, pure Mg is added into melt, after furnace charge all fusing, by furnace
Temperature drop is kept the temperature to 720 DEG C；After furnace temperature is stablized, slag is taken off, tetrachloroethanes is added and carries out degassing processing, is added after the completion of degasification
Coverture is covered with, and the refining of aluminium refining agent is then added in two portions, and skimming after keeping the temperature at 720 DEG C obtains refined metals melt；It is quiet
It after setting 20min, is poured into graphite jig, carries out cooling treatment；
Three, hot-working and heat treatment
Homogenization Treatments: slab is kept the temperature 24 hours at 465 DEG C, is then carried out air-cooled；
Heat treatment: by the alloy after homogenization in 450 DEG C of progress hot rollings, rolling cumulative deformation is 90%, divides 5
Secondary, cumulative deformation carries out intermediate annealing when reaching 60%, and annealing temperature is 450 DEG C, annealing time 5min；
Solution treatment: room temperature water is carried out after keeping the temperature 2 hours at 480 DEG C and is quenched；
Ageing treatment: after solution treatment, through being air-cooled to room temperature after heat preservation different time at 150 DEG C；
Four, performance and structure observation
By the alloy sampling of different time ageing treatment at 150 DEG C, tensile tests at room test intensity and elongation percentage, test
As a result as shown in specification subordinate list 1.Table 1 is the results show that the thermal stability of the comparative example alloy without Co addition is poor.At 150 DEG C
Effect 50 hours, tensile strength has dropped~8% compared with its peak timeliness intensity (650MPa), is 580MPa；After timeliness 108 hours,
Intensity has dropped~15% compared with peak timeliness, is 550MPa.To alloy in 150 DEG C of samples after timeliness 50 hours, respectively into
Row transmission electron microscope tissue characterization, as a result as shown in Fig. 2, the results show that 150 DEG C of alloy timeliness 6 hours, crystal boundary, matrix precipitate
Equal small and dispersed；After timeliness 50 hours, crystal boundary, matrix precipitate have occurred obviously to be roughened, and crystal boundary continuous crystal boundary occurs and is precipitated
Phase, it is meant that alloy strength and anti-stress corrosion performance reduce simultaneously.
Embodiment 1 (aluminium alloy of lower Co content and lower solute total amount)
One, alloying component matches
Total soluble matters content (Zn+Mg+Cu+Co+Zr)=12.32%
Two, founding:
A) control smelting temperature is 740~760 DEG C, will be closed among corresponding pure Al, Zn, Cu metal charge and Al-Zr
Gold is melted under the conditions of 760 DEG C, and electromechanical stirring then passes through the processing of chlorine hydrogen gaseous mixture refining techniques and melt filtration；
B) Mg and Co pieces are added in 730 DEG C of temperature ranges to filtered melt, be sufficiently stirred after fusing, filter and
Chlorine hydrogen gaseous mixture refining treatment, sufficient standing 25min or more after refining；
C) when temperature is down to 720 DEG C, the alloy melt after sufficient standing is directly poured, is continuously or semi-continuously cast
It makes；
Three, hot-working and heat treatment
Homogenization: slab is kept the temperature 24 hours at 465 DEG C, is then carried out air-cooled；
Thermal deformation: by the alloy after homogenization in 450 DEG C of progress hot rollings, rolling cumulative deformation is 90%, point 5 passages,
Cumulative deformation carries out intermediate annealing when reaching 60%, annealing temperature is 450 DEG C, annealing time 5min；
Solution treatment: room temperature water is carried out after keeping the temperature 2 hours at 480 DEG C and is quenched；
Ageing treatment: after solution treatment, through being air-cooled to room temperature after heat preservation different time at 150 DEG C；
Four, performance test
By the alloy sampling at 150 DEG C through different time ageing treatment, tensile tests at room test intensity and elongation percentage are surveyed
Test result is as shown in specification subordinate list 1.Table 1 is the results show that behind at 150 DEG C progressive aging 84 hours, and tensile strength is compared with its peak
Aging strength (653MPa) decline~8% is 600MPa.Compared with the comparative example alloy of no Co content, embodiment 1 alloy heat is steady
It is qualitative to improve 60%.Tensile strength decline~10% after 108 hours, is 586MPa.Elongation after fracture is increased to by 8.9%
9.6%, it is suitable with the comparative example alloy of no Co content.
Embodiment 2 (aluminium alloy of higher Co content and lower solute total amount)
One, alloying component matches:
Total soluble matters content (Zn+Mg+Cu+Co+Zr)=15.62%
Two, alloy melting: consistent with embodiment 1；
Three, hot-working and heat treatment: consistent with embodiment 1；
Four, performance and structure observation
By the alloy sampling of different time ageing treatment at 150 DEG C, tensile tests at room test intensity and elongation percentage, test
As a result as shown in specification subordinate list 1.Table 1 is the results show that alloy prepared by the present invention has superhigh intensity, and thermal stability is good
It is good.At 150 DEG C after progressive aging 84 hours, intensity only declines~4% compared with its peak timeliness intensity (762MPa), be 732MPa, 108
Intensity after hour also only declines~8%, is 698MPa.Compared with the comparative example alloy of no Co content, embodiment 2 alloy heat is steady
It is qualitative to improve 100%.Elongation after fracture is increased to 7.7% by 6.5%, to alloy in 150 DEG C of samples after timeliness 50 hours
Sampling carries out transmission electron microscope tissue characterization, as a result as shown in Figure 3 respectively.Fig. 3 is the results show that matrix precipitate still keeps tiny
Disperse, Grain Boundary Precipitates start to be roughened but still remain open, and continuous Grain Boundary Precipitates do not occur, this shows the conjunction
Gold still keeps superhigh intensity (720MPa), and has both good anti-stress corrosion performance.
1 embodiment of the present invention of table and comparative example alloy are compared through the mechanical property of 150 DEG C of timeliness different times
From the above results it can be seen that using novel alloy ingredient of the present invention, it can through the preparation process
It realizes the above superhigh intensity of tensile strength 750MPa, and is able to maintain 92% peak strength up to 100 hours or more, elongation percentage
High thermal stability ultra-high-strength aluminum alloy greater than 7.5%.The novel 7 line aluminium alloy material of the present invention containing Co, using routine
Founding+thermal deformation+heat treatment method, it can be achieved that high thermal stability 750MPa grade super strength, and have good anti-answer
Power corrosive nature and preferable formability, this undoubtedly will be helpful to expand ultra-high-strength aluminum alloy in aerospace, traffic fortune
The application range of the various fields such as defeated and weapon industry.
Claims (5)
1. a kind of high thermal stability ultra-high-strength aluminum alloy is made of by weight percentage following components: Zn content is 8~14%,
It is 0.3~2%, Co content be 0.2~2.0%, Zr content is 0.1~0.3% that Mg content, which is 1.8~3%, Cu content, impurity
Elements Si content≤0.08%, Impurity Fe≤0.1%, remaining content of impurities≤0.1%, remaining is aluminium.
2. the preparation method of high thermal stability ultra-high-strength aluminum alloy according to claim 1, which is characterized in that including following step
It is rapid:
(1) it stocks up: carrying out ingredient according to the design component of alloy, prepare melting；
Wherein Al, Zn, Mg, Cu, Co are pure metal, and Al-Zr is intermediate alloy；
(2) founding: smelting temperature is 740~760 DEG C, and Al, Zn, Cu and Al-Zr intermediate alloy is added, and standing of skimming is being set
At a temperature of Mg, Co are added into melt, cast after standing, casting taken out after solidifying completely；
(3) it homogenizes: carrying out Homogenization Treatments in Muffle furnace, homogenization temperature is 460 ± 50 DEG C, and the time is 24~36h；
(4) thermal deformation: heat distortion temperature is 450 ± 50 DEG C, cumulative deformation > 70%；
(5) solution treatment: alloy after thermal deformation carries out solution treatment, and solution annealing temperature is 480 ± 50 DEG C, and the time is 2~
4h then carries out water quenching；
(6) ageing treatment: the alloy after solid solution is heated at 120~150 DEG C, carries out ageing treatment.
3. the preparation method of high thermal stability ultra-high-strength aluminum alloy according to claim 2, which is characterized in that in step (1),
The pure metal and Al-Zr intermediate alloy are preheated, preheating temperature is 120~150 DEG C, and preheating time is 1~2h.
4. the preparation method of high thermal stability ultra-high-strength aluminum alloy according to claim 2, which is characterized in that the step
(2) founding in, specifically:
A) control smelting temperature is 740~760 DEG C, and corresponding pure Al, Zn, Cu metal charge and Al-Zr intermediate alloy are existed
It is melted under the conditions of 760 DEG C, electromechanical stirring then passes through the processing of chlorine hydrogen gaseous mixture refining techniques and melt filtration；
B) Mg and Co pieces are added in 730 DEG C of temperature ranges to filtered melt, is sufficiently stirred, filters and chlorine hydrogen after fusing
Gaseous mixture refining treatment, sufficient standing 25min or more after refining；
C) when temperature is down to 720 DEG C, the alloy melt after sufficient standing is directly poured, is continuously or semi-continuously cast.
5. the preparation method of high thermal stability ultra-high-strength aluminum alloy according to claim 2, which is characterized in that in step (6),
Institution of prescription is that 12~50h is kept the temperature at 150 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111014683A (en) * | 2019-12-05 | 2020-04-17 | 中南大学 | Heat treatment process for 3D printing of scandium-containing zirconium-aluminum alloy |
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| RU2215807C2 (en) * | 2001-12-21 | 2003-11-10 | Региональный общественный фонд содействия защите интеллектуальной собственности | Aluminum-base alloy, article made of thereof and method for making article |
| CN101413079A (en) * | 2008-09-17 | 2009-04-22 | 北京有色金属研究总院 | Cobaltiferous aluminum alloy material and preparation thereof |
| CN101509091A (en) * | 2009-03-27 | 2009-08-19 | 中南大学 | High-strength high-ductility Al-Zn-Mg-Cu-Sr alloy and production method |
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2019
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2215807C2 (en) * | 2001-12-21 | 2003-11-10 | Региональный общественный фонд содействия защите интеллектуальной собственности | Aluminum-base alloy, article made of thereof and method for making article |
| CN101413079A (en) * | 2008-09-17 | 2009-04-22 | 北京有色金属研究总院 | Cobaltiferous aluminum alloy material and preparation thereof |
| CN101509091A (en) * | 2009-03-27 | 2009-08-19 | 中南大学 | High-strength high-ductility Al-Zn-Mg-Cu-Sr alloy and production method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111014683A (en) * | 2019-12-05 | 2020-04-17 | 中南大学 | Heat treatment process for 3D printing of scandium-containing zirconium-aluminum alloy |
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