CN109468496A - A kind of heat-proof compression casting aluminium alloy and preparation method thereof - Google Patents

A kind of heat-proof compression casting aluminium alloy and preparation method thereof Download PDF

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Publication number
CN109468496A
CN109468496A CN201811625450.4A CN201811625450A CN109468496A CN 109468496 A CN109468496 A CN 109468496A CN 201811625450 A CN201811625450 A CN 201811625450A CN 109468496 A CN109468496 A CN 109468496A
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aluminium alloy
preparation
heat
temperature
aluminium
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CN109468496B (en
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陈曦
汪时宜
周银鹏
徐欣
罗云斌
赵华
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Suzhou Hui Jin New Mstar Technology Ltd
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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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/026Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/03Making non-ferrous alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention belongs to technical field of aluminum alloy technology, a kind of heat-proof compression casting aluminium alloy and preparation method thereof is more particularly related to.Each raw material weight proportioning of soup processed is Ce:0.5wt%-3wt% in heat-proof compression casting aluminium alloy of the present invention;B < 0.05wt%;Fe:0.5wt%-3wt%;Sc < 0.5wt%;Cu < 0.5wt%, surplus are Al and inevitable impurity.The present invention adds Ce, Sc, B and Cu on the basis of Al-Fe, and the mechanical property that can be obviously improved at the room temperature and 300 DEG C of pack alloy prepares heat-proof compression casting aluminium alloy.

Description

A kind of heat-proof compression casting aluminium alloy and preparation method thereof
Technical field
The invention belongs to technical field of aluminum alloy technology, a kind of heat-proof compression casting aluminium alloy and preparation method thereof is more particularly related to.
Background technique
Aluminium alloy is widely used in each industry neck because of its low-density, high specific strength, excellent ductility, corrosion resistance Domain.With the development of science and technology, the fields such as high-speed rail, aerospace, weapons constantly put forward higher requirements aluminium alloy, tradition Al-Si, Al-Cu, Al-Zn and Al-Mg alloy be difficult to adapt to harsh environment.Modern sky day application requirement aluminium alloy tool Standby high-temperature stability;But many aluminium alloys are higher than T in temperaturem/2(TmFor aluminium alloy fusing point) when can cause because of temperature factor Dispersed granules and crystal grain are grown up, its performance is greatly reduced.
The production principle of high temperature alloy: solid solubility of the alloying element in aluminium is small, and the diffusion in solid aluminum is slow, it is ensured that closes A large amount of undissolved Second Phase Particles are formed in gold, there is very strong heat resistance, and brilliant power is prevented to grow up.It is closed in aluminium-iron class casting The intermetallic compound Al that Jin Zhong, transition-metal Fe and Al chemical combination are formed3Fe has excellent heat resistance.However, Fe is in aluminium The content of matrix is once more than its solid solubility limit, just will form the Fe-riched phase of fine acicular, coarse sheet, seriously isolates matrix, makes It is concentrated at stress, so that aluminium alloy mechanical behavior under high temperature drastically reduces.
Thus, the present invention is by adding different alloying elements, under conditions of guaranteeing cast performance, by micro The addition of element and purification element, further to promote the heat resistance of aluminum alloy materials.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of heat-proof compression casting aluminium to close Gold and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions: a kind of heat-proof compression casting aluminium alloy, by weight percentage It include the following raw material: Ce:0.5wt%-3wt% than calculating;B < 0.05wt%;Fe:0.5wt%-3wt%;Sc < 0.5wt%;Cu < 0.5wt%, surplus are Al and inevitable impurity;The inevitable impurity is controlled in 0.05wt% or less.
According to another aspect of the present invention, the present invention provides a kind of preparation methods of heat-proof compression casting aluminium alloy, including Following steps:
1) quality of intermediate alloy needed for calculating according to the ratio, stocks up;
2) after aluminium ingot surface clean is clean, aluminium ingot is put into smelting furnace or shaft furnace crucible and carries out melting, smelting temperature It is 690-710 DEG C;
3) when temperature of aluminum liquid reaches 750 DEG C, Fe, Cu after drying are added in molten aluminum, keep the temperature 15-20min;
4) commercially available Ce, Sc and B are mixed with metallic powder with Al powder, in gained mixture Al powder weight with Ce, Sc, B powder weight and equal, is subsequently placed in high frequency heating furnace, is heat-treated 10~30min, is directly added into molten aluminum;
5) raw material all fusing after, it is successively refined, pull out slag, casting, obtain aluminium alloy castings.
Preferably, Cu described in step 3) is with the addition of pure Cu formula, specifically: it is 10mm that commercially available pure Cu, which is processed as side length, Cube, after 110 DEG C of dryings with metal aluminum foil by its all package wherein, after addition with pressing plate under 300-500MPa pressure It is completely forced into molten aluminum.
Preferably, Fe is added in the form of chalybeate in aluminium alloy described in step 3): molten aluminum is warming up to 780-800 DEG C Afterwards, commercially available chalybeate is direct plungeed into molten aluminum, keeps the temperature 30min.
Preferably, high frequency, that is, high frequency waves described in step 4), high frequency refer to that frequency is greater than the electromagnetic wave of 100Khz, Ce, Sc, B and Al metal powder activate positively charged molecule under the action of high-frequency electromagnetic, make between each metalliferous material interior molecules mutually Fierceness collision generates high temperature, melting mixing.Using high frequency heating means, so that B and impurity element is formed boride and be transformed into analysis State out, impurity are reduced.Meanwhile under the action of high-frequency electromagnetic, remaining Fe is formed in Ce, Sc and Al and Al metal powder Al13Fe3Ce and Al3Sc。
Preferably, refining described in step 5) is to be carried out under the conditions of 720 DEG C using the dedicated refining agent of aluminium alloy;Refining After be cooled to 700 DEG C of heat preservations, stand 5 minutes, so that field trash is adequately floated or is sunk, then carry out pulling out slag;Then 700 DEG C when alterant be added carry out Metamorphism treatment, stand 10 minutes after stirring sufficiently, pull out slag after standing, remove surface scale and bottom Portion's impurity.
Preferably, the dedicated refining agent of the aluminium alloy uses upper marine rainbow light Metal Melting factory, and HGJ-2 aluminium alloy is without sodium essence Refine slag-cleaning agent.
Preferably, the temperature of aluminum liquid after refining, being rotten is down to 680 DEG C of preparation casting by step 5), using metal gravity Pouring technology, casting mold are warming up to 200 DEG C in an oven, and molten aluminum is added among mold with scoop and is formed.
Compared with prior art, the invention has the following advantages:
1. added in aluminum substrate micro B can be allowed to its micro impurity element, such as: Ti, Cr, Mn, V etc., reaction Boride is generated, such as: TiB2, CrB2, CaB6Deng each boride is transformed into precipitation state by solid solution state, and the lattice in aluminum substrate is abnormal Change degree weakens, to effectively improve the thermal stability of aluminum substrate.
2. since cerium and scandium atomic radius are greater than aluminium, if can cause great distortion of lattice into aluminium lattice, make rare earth Energy increases.Therefore, to keep the free energy of rare earth minimum, rare earth atom can only be rich as the irregular grain boundaries of atomic arrangement Collection, it will with Sync enrichment in the grain boundaries of aluminum substrate, form Al13Fe3Ce and Al3The second phase of Sc, both are with Gao Rong Second phase of point, can be further improved the heat resistance of aluminium alloy.
3. cerium and scandium can be preferentially adsorbed on around Fe-riched phase, on the one hand, the movement of Fe atom can be hindered, increase Fe The concentration of atom causes constitutional supercooling, and on the other hand, the enrichment of rare earth element hinders the continued growth of Fe-riched phase.Cerium and scandium It is added, Fe-riched phase becomes corynebacterium, spherical Sc and flower, tiny needle bar shape by coarse gill shape, to improve Fe-riched phase The distributing homogeneity in aluminum substrate, refine crystal grain, alleviate stress concentration, improve Al-Fe alloy high-temp mechanical property.
4. the content of strict control Cu within 0.5wt%, makes material internal form the CuAl of micro disperse2Second phase, The high-temperature stability of further reinforced aluminium alloy.
Specific embodiment
Embodiment
A kind of hot thin-walled pack alloy of high-strength highly-conductive, the ingredient including weight percentage described in following table 1, surplus are Aluminium and inevitable impurity.
Ce:0.5wt%-3wt%;B < 0.05wt%;Fe:0.5wt%-3wt%;Sc < 0.5wt%;Cu < 0.5wt%, Remaining inevitable impurity is all controlled in 0.05wt% hereinafter, surplus is Al and inevitable impurity.
Table 1 is each element weight content table in the aluminium alloy of embodiment 1-15
Embodiment Ce B Fe Cu Sc
1 0 0 0.6 0.2 0
2 0 0 1.50 0.15 0
3 0 0 2.61 0.25 0
4 1.04 0.03 1.72 0.31 0
5 1.22 0.01 1.73 0.34 0.15
6 1.65 0.04 1.77 0.43 0.21
7 1.18 0.02 1.69 0.43 0.23
8 2.28 0.03 2.64 0.32 0.25
9 2.42 0.05 2.6 0.27 0.34
10 2.23 0.02 2.55 0.33 0.38
11 2.13 0.01 2.58 0.17 0.41
12 2.62 0.03 2.46 0.44 0.48
13 3.13 0.02 3.32 0.37 0.35
14 3.45 0.03 3.56 0.31 0.41
15 3.67 0.02 3.74 0.24 0.35
Aluminium alloy described in the various embodiments described above the preparation method comprises the following steps:
1) quality of intermediate alloy needed for calculating according to the ratio, stocks up;
2) after aluminium ingot surface clean is clean, aluminium ingot is put into smelting furnace or shaft furnace crucible and carries out melting, smelting temperature It is 690-710 DEG C;
3) when temperature of aluminum liquid reaches 750 DEG C, Fe, Cu after drying are added in molten aluminum, keep the temperature 15-20min;Wherein The adding manner of Cu intermediate alloy are as follows: commercially available Cu intermediate alloy is processed as the cube that side length is 10mm, is used after 110 DEG C of dryings By it, all package wherein, is completely forced into molten aluminum under 300-500MPa pressure after addition with pressing plate, Fe metal aluminum foil Adding manner are as follows: commercially available chalybeate is pressed into the laminar plate with a thickness of 2-3mm in advance, then is put into molten aluminum;
4) commercially available Ce, Sc and B are mixed with metallic powder with Al powder, in gained mixture Al powder weight with Ce, Sc, B powder weight and equal, is subsequently placed in high frequency heating furnace, is heat-treated 10~30min, is directly added into molten aluminum;
5) raw material all fusing after, it is successively refined, pull out slag, casting, obtain aluminium alloy castings.The refining be Under the conditions of 720 DEG C, carried out using the dedicated refining agent of aluminium alloy;It is cooled to 700 DEG C of heat preservations after refining, stands 5 minutes, makes field trash It adequately floats or sinks, then carry out pulling out slag;Then alterant is added at 700 DEG C and carries out Metamorphism treatment, stirring is abundant 10 minutes are stood afterwards, slag is pulled out after standing, removes surface scale and impurities at bottom.The dedicated refining agent of the aluminium alloy is using upper Marine rainbow light Metal Melting factory, HGJ-2 aluminium alloy refine slag-cleaning agent without sodium.Temperature of aluminum liquid after refining, being rotten is down to 680 DEG C of standards Standby casting, using metal gravity pouring technology, casting mold is warming up to 200 DEG C in an oven, is added to molten aluminum with scoop It is formed among mold.
Mechanical experimental results of the aluminium alloy castings sample of 2 embodiment 1-15 of table at room temperature and 300 DEG C
As can be seen from Table 2, Ce, Sc, B and Cu are added on the basis of Al-Fe, can be obviously improved the room of pack alloy Mechanical property at mild 300 DEG C, and as the content of Ce and Fe in aluminium alloy increases, the mechanical property of room temperature and high temperature It obtains continuing improvement, the content of Ce and Fe are more than 3wt%, unobvious to the mechanical property improvement of pack alloy.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (8)

1. a kind of heat-proof compression casting aluminium alloy, it is characterised in that: count by weight percentage, including the following raw material: Ce:0.5wt%- 3wt%;B < 0.05wt%;Fe:0.5wt%-3wt%;Sc<0.5 wt%;Cu < 0.5wt%, surplus is for Al and inevitably Impurity;The inevitable impurity is controlled in 0.05wt% or less.
2. a kind of preparation method of heat-proof compression casting aluminium alloy described in claim 1, it is characterised in that: include the following steps,
1) quality of intermediate alloy needed for calculating according to the ratio, stocks up;
2) after aluminium ingot surface clean is clean, aluminium ingot is put into smelting furnace or shaft furnace crucible and carries out melting, smelting temperature is 690-710℃;
3) when temperature of aluminum liquid reaches 750 DEG C, Fe, Cu after drying are added in molten aluminum, keep the temperature 15-20min;
4) Ce, Sc and B are mixed with metallic powder with Al powder, Al powder weight and Ce, Sc, B in gained mixture Powder weight and equal, is subsequently placed in high frequency heating furnace, is heat-treated 10 ~ 30min, is directly added into molten aluminum;
5) raw material all fusing after, it is successively refined, pull out slag, casting, obtain aluminium alloy castings.
3. preparation method according to claim 2, it is characterised in that: Cu described in step 3) is with the addition of pure Cu formula, tool Body adds step are as follows: pure Cu is processed as the cube that side length is 10mm, is all wrapped up it with metal aluminum foil after 110 DEG C of dryings Wherein, it is completely forced into molten aluminum under 300-500MPa pressure after addition with pressing plate.
4. preparation method according to claim 2, it is characterised in that: Fe is in aluminium alloy described in step 3) with the shape of chalybeate Formula addition, specifically adds step are as follows: after molten aluminum is warming up to 780-800 DEG C, chalybeate is direct plungeed into molten aluminum, keeps the temperature 30min.
5. preparation method according to claim 2, it is characterised in that: high frequency, that is, high frequency waves described in step 4), high week Wave refers to that frequency is greater than the electromagnetic wave of 100Khz.
6. preparation method according to claim 2, it is characterised in that: refining described in step 5) be under the conditions of 720 DEG C, It is carried out using the dedicated refining agent of aluminium alloy.
7. preparation method according to claim 5, it is characterised in that: the dedicated refining agent of aluminium alloy uses upper marine rainbow light Metal Melting factory, HGJ-2 aluminium alloy refine slag-cleaning agent without sodium.
8. preparation method according to claim 2, it is characterised in that: the temperature of aluminum liquid after refining, being rotten drops in step 5) It is poured to 680 DEG C of preparations, using metal gravity pouring technology, casting mold is warming up to 200 DEG C in an oven, with scoop by aluminium Liquid is added among mold and forms.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110373574A (en) * 2019-07-18 2019-10-25 上海交通大学 A kind of nearly cocrystallizing type high-strength temperature-resistant Al-Ce line aluminium alloy and preparation method
CN110484757A (en) * 2019-07-18 2019-11-22 上海交通大学 A kind of high conductivity and heat heat resistance in-situ authigenic aluminum matrix composite and preparation method
CN114015911A (en) * 2021-10-18 2022-02-08 柳州市智甲金属科技有限公司 Die-casting rare earth aluminum alloy and preparation method thereof
CN117535565A (en) * 2024-01-09 2024-02-09 苏州慧金新材料科技有限公司 High-conductivity die-casting aluminum alloy based on dispersion strengthening and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570877A (en) * 1991-09-13 1993-03-23 Takeshi Masumoto Aluminum alloy material having high strength and high toughness and its production
CN102719709A (en) * 2012-05-17 2012-10-10 深圳市兆方创业科技有限公司 Aluminium alloy wire with high strength and high electrical conductivity, and preparation method thereof
CN107739916A (en) * 2017-12-04 2018-02-27 苏州慧驰轻合金精密成型科技有限公司 A kind of hot thin-walled pack alloy of high-strength highly-conductive and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570877A (en) * 1991-09-13 1993-03-23 Takeshi Masumoto Aluminum alloy material having high strength and high toughness and its production
CN102719709A (en) * 2012-05-17 2012-10-10 深圳市兆方创业科技有限公司 Aluminium alloy wire with high strength and high electrical conductivity, and preparation method thereof
CN107739916A (en) * 2017-12-04 2018-02-27 苏州慧驰轻合金精密成型科技有限公司 A kind of hot thin-walled pack alloy of high-strength highly-conductive and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110373574A (en) * 2019-07-18 2019-10-25 上海交通大学 A kind of nearly cocrystallizing type high-strength temperature-resistant Al-Ce line aluminium alloy and preparation method
CN110484757A (en) * 2019-07-18 2019-11-22 上海交通大学 A kind of high conductivity and heat heat resistance in-situ authigenic aluminum matrix composite and preparation method
CN110373574B (en) * 2019-07-18 2020-09-25 上海交通大学 Near-eutectic high-strength heat-resistant Al-Ce aluminum alloy and preparation method thereof
CN114015911A (en) * 2021-10-18 2022-02-08 柳州市智甲金属科技有限公司 Die-casting rare earth aluminum alloy and preparation method thereof
CN117535565A (en) * 2024-01-09 2024-02-09 苏州慧金新材料科技有限公司 High-conductivity die-casting aluminum alloy based on dispersion strengthening and preparation method and application thereof
CN117535565B (en) * 2024-01-09 2024-04-26 苏州慧金新材料科技有限公司 High-conductivity die-casting aluminum alloy based on dispersion strengthening and preparation method and application thereof

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