CN106756276A - A kind of cast aluminium alloy gold Al Ti B Y Ce fining agents and its preparation method and application - Google Patents

A kind of cast aluminium alloy gold Al Ti B Y Ce fining agents and its preparation method and application Download PDF

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Publication number
CN106756276A
CN106756276A CN201611183562.XA CN201611183562A CN106756276A CN 106756276 A CN106756276 A CN 106756276A CN 201611183562 A CN201611183562 A CN 201611183562A CN 106756276 A CN106756276 A CN 106756276A
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powder
aluminium
alloy
aluminium alloy
cast aluminium
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张松利
印厚尚
张炳荣
张冬梅
张倩
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Zhenjiang Powerise Special Alloy Technology Development Co Ltd
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Zhenjiang Powerise Special Alloy Technology Development Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making 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 alloys
    • C22C1/02Making alloys by melting
    • C22C1/03Making alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/06Making alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium

Abstract

The present invention proposes a kind of cast aluminium alloy gold Al Ti B Y Ce fining agents and its preparation method and application.The mass percent of the Al Ti B Y Ce fining agents of preparation is:Ti is that 3.5% ~ 5.5%, B is that 0.5% ~ 1.5%, Y is that 0.05% ~ 0.25%, Ce is 0.1% ~ 0.3%, balance of Al.This method preparation process is simple, can accurately control the composition of fining agent.Crystal grain refinement is carried out to cast aluminium alloy gold using the fining agent, Ce and Y element are filled up in α Al dendrites and Eutectic Silicon in Al-Si Cast Alloys interface, hinder α Al dendrite growths, and can refine thick piece strip eutectic silicon in cast aluminium alloy gold.In addition the reciprocation of Ce elements and Y element is more notable to cast aluminium alloy gold thinning effect than Rare Earth Elements Determination fining agent.

Description

A kind of cast aluminium alloy gold Al-Ti-B-Y-Ce fining agents and its preparation method and application
Technical field
The invention belongs to metal material field, it is related to a kind of be applicable to fining agent of cast aluminium alloy gold and preparation method thereof And application.
Background technology
Aluminium alloy has excellent casting character, heat treatment performance, cold-forming property, fatigue behaviour and good intensity And plasticity, it is wide using scope, it is the indispensable materials of industry such as current many dual-use vehicles, house ornamentation, in national defence Build and there is important strategic position in the national economic development.Wherein aluminium silicon systems casting alloy is in automobile, the firm system of motor vehicle wheel Make and be of wide application in industry.It is general in industrial production to use casting technique base, because alloying level is high, two phase region , easily there are coarse grains in width, and a large amount of non-equilibrium eutecticum tissues can be produced in crystal boundary and dendrite circle, and dendritic segregation is serious, have impact on The following process of ingot casting and the tissue of product and performance.
As the increase that Si in alloy is measured, Eutectic Silicon in Al-Si Cast Alloys also increase in alusil alloy, Si phases are presented gill shape, seriously isolate Aluminum substrate, produces stress concentration at the tip of Si phases, and alloy easily ftractures in grain boundaries, alloy is become fragile, and mechanical property and cuts Cut processing characteristics reduction.Therefore, in alusil alloy, when silicone content is higher than 6%, it is necessary to carry out fine degenerate treatment.At fine degenerate Reason makes crystal grain refinement, makes that eutectic Si becomes fiber fines shape by thick sheet or lamellar is evenly distributed on aluminum substrate, from And improve alloy property.
The thinning method of aluminium alloy is mainly fining agent is added in aluminum melt, and the fining agent commonly used in production at present has Al-5Ti, Al-Ti-B, Al-Ti-C etc., wherein Al-5Ti, Al-Ti-B are most widely used.For conventional Al-Ti-B refiner Some for existing lack:TiB2Particle easily assembles, precipitate and lose grain refining efficiency;Easily there is toxic reaction in B, lose refinement with Cr, Zr Ability;TiB in conventional fining agent2, Al3Ti particles, can be as effective heterogeneous forming core core less than 1%, grain refining efficiency Have much room for improvement.
Retrieval discovery to prior art literature, China Patent No. 201210056875(A kind of title " aluminium Al-Ti-B The preparation method of Master alloy refiners ")The patented technology is that Ti powder, boric acid, fluorine boron are added in the aluminum melt of higher temperature Sour potassium and potassium chloride, continuously stir for a long time, obtain aluminium alloy fining agent.But preparation method can be produced during melting Toxic gas, also has corrosiveness to crucible.There is certain limitation in the preparation technology, the performance of prepared aluminium alloy needs Further improve.China Patent No. 201110397093.2(" a kind of aluminum alloy modifier and its adding method "), the patent is After alloy refining is finished, alterant is added under protective gas effect, and technique is cumbersome, and cost increases.
Researcher has carried out substantial amounts of research to aluminium alloy fining agent, and research both at home and abroad finds rare earth Sc, La etc., with thin Change the effect of crystal grain, being primarily due to rare earth element has larger segregation coefficient, and easy segregation, forms larger in process of setting Constitutional supercooling, refined crystal grain;The segregation easily at crystal boundary, phase boundary, hinders growing up for crystal grain, has refined crystal grain.Rare earth unit Element has suction-operated, can effectively adsorb interstitial atom O, N, H etc., plays catharsis." rare earth is in the middle of Al-Ti-B-RE Effect in alloy "(Zhang Shenghua, Zhang Han, Zhu Yun bis-, Central South University's journal(Natural science edition). 2005, 36 (3) :386- 388 ), have studied rich Ce rare earths and Al-Ti-B is organized and thinning effect influence, it is found that rare earth can improve Al3Ti and TiB2Grain The distribution of son, reduces its size, improves its thinning effect;" tissue characteristic of aluminium-titanium-horon rare earth fining agent "(Li Zhiyang, Ni Hong Army, Wang Xingxing, Zhu Xing, the foundry engieering .2012. 32 (1) of yellow bright space two: 20-22), rich Ce rare earths are have studied to technical pure The influence of aluminium refinement, it is found that rare earth can extend the fading of refinement time of Al-Ti-B.Rare earth element is added in Al-Ti-B such as Y, Ce etc., improve Al in fining agent3Ti, TiB2The size of particle, pattern, distribution, can obtain the fining agent of good quality.
The content of the invention
The invention provides a kind of cast aluminium alloy gold Al-Ti-B-Y-Ce fining agents and its preparation method and application.Solve TiB2Particle is easily assembled, B easily occurs toxic reaction with Cr, Zr, loses the problem of grain refining efficiency and extends the thin of Al-Ti-B Change fall time.The technology path for solving the above problems is the Y and Ce for adding different content, prepares a kind of composite modifying-refining Agent.
A kind of cast aluminium alloy gold includes following mass percent component with Al-Ti-B-Y-Ce fining agents:Ti be 3.5% ~ 5.5%, B are that 0.5% ~ 1.5%, Y is that 0.05% ~ 0.25%, Ce is 0.1% ~ 0.3%, balance of Al.
A kind of above-mentioned cast aluminium alloy gold Al-Ti-B-Y-Ce fining agents and its preparation method and application, it is characterised in that Ti, B are with TiO2Powder, B2O3Powder is added, and Y, Ce are added in intermediate alloy form, is prepared using melting-reaction method, is specifically included following Step:
(1)Raw material prepares, and aluminium powder, TiO are weighed on request2Powder, B2O3Powder, Al-Y alloys, Al-Ce alloys, aluminium ingot, it is desirable to nAl powder : nTiO2Powder: nB2O3Powder=6:(1.5~2.5):(1.2~1.5), aluminium ingot purity 99. 9%;
(2)By aluminium powder, TiO2Powder and B2O3Powder, be put into vacuum ball grinder, by certain ratio of grinding media to material under certain rotating speed high energy Ball milling for a period of time, well mixed powder is placed in mould, is pressed into block;
(3)Aluminium ingot is put into the resistance furnace that power is 10kW, is heated to being completely melt, melt temperature is controlled at 800 DEG C -900 DEG C, cover one layer of ice crystal coverture, graphite bell jar press-in step(2)Block, graphite rod uniform stirring, react l5min;Instead After the completion of answering, 730 DEG C ~ 750 DEG C are cooled to;Graphite bell jar is pressed into Al-Ce, Al-Y intermediate alloy, 10min is stood, until middle Alloy is completely melt and spreads uniform;Press-in C2Cl6, refine, skim, aluminum melt is poured into warmed-up 200 DEG C of swage In, obtain Al-Ti-B-Y-Ce modifying-refining agents.
Above-mentioned aluminium powder is 200 mesh, TiO2Powder is 300 mesh, B2O3Powder is 325 mesh.Step(2)In certain ratio of grinding media to material it is preferred (7~10):1, certain rotating speed preferably 250 ~ 400rpm, a period of time preferably 6 ~ 8h.
In another aspect of the present invention, there is provided according to fining agent micronization processes prepared by previously described preparation method The method of AlSi9Cu1 cast aluminium alloy golds.
Brief description of the drawings
Fig. 1 is the light of the Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerate AlSi9Cu1 aluminium alloys that implementation method 2 is obtained Mirror figure.As seen from the figure, α-Al crystal grain is tiny, and alloy structure is uniform.
Fig. 2 is the Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerate AlSi9Cu1 Aluminum alloy tensiles that implementation method 2 is obtained The tensile stress-strain curve comparison diagram of the AlSi9Cu1 alloys of load-deformation curve and non-fine degenerate.
Specific embodiment
Technical solution of the present invention is not limited to act specific embodiment set forth below, also including between each specific embodiment Any combination.
Implementation method 1:
A kind of cast aluminium alloy gold of present embodiment Al-Ti-B-Y-Ce fining agents and its preparation method and application are by following What step was realized:
(1)Raw material prepares, and prepares Al-Ti-B-Y-Ce fining agents and includes following mass percent component:Ti is that 4%, B is 1.2%, Y are that 0.1%, Ce is 0.2%, balance of Al;Aluminium powder, TiO are weighed on request2Powder, B2O3Powder, Al-Y alloys, Al-Ce are closed Gold, aluminium ingot, it is desirable to nAl powder: nTiO2Powder: nB2O3Powder=6:2:1, aluminium ingot purity 99. 9%;
(2)By aluminium powder, TiO2Powder and B2O3Powder, it is put into vacuum ball grinder, by ratio of grinding media to material 8:1, the high energy ball under rotating speed 300rpm Mill 6h, well mixed powder is placed in mould, is pressed into block;
(3)Aluminium ingot is put into the resistance furnace that power is 10kW, is heated to being completely melt, melt temperature is controlled at 800 DEG C -900 DEG C, cover one layer of ice crystal coverture, graphite bell jar press-in step(2)Block, graphite rod uniform stirring, react l5min;Instead After the completion of answering, 730 DEG C ~ 750 DEG C are cooled to;Graphite bell jar is pressed into Al-Ce, Al-Y intermediate alloy, 10min is stood, until middle Alloy is completely melt and spreads uniform;Press-in C2Cl6, refine, skim, aluminum melt is poured into warmed-up 200 DEG C of swage In, obtain Al-4Ti-1.2B-0.1Y-0.2Ce modifying-refining agents.
Thinning effect compares:
The condition of crystal grain refinement treatment is carried out to AlSi9Cu1 aluminium alloys:It is the graphite crucible resistance furnace melting of 10kW to use power AlSi9Cu1 aluminium alloys, after alloy is completely melt, cool the temperature to 750 DEG C, are incubated l0min, skim.Treat that melt temperature is down to At 730 DEG C, the Al-4Ti-1.2B-0.1Y-0.2Ce fining agents of 0.1wt% are added, stand 10min, skimmed, finally pour melt In the copper mould of 200 DEG C of injection preheating.The AlSi9Cu1 aluminium alloys of gained Al-4Ti-1.2B-0.1Y-0.2Ce fine degenerates with The AlSi9Cu1 aluminium alloys of non-fine degenerate carry out the comparing of microstructure and mechanical property.
Implementation method 2:
A kind of cast aluminium alloy gold of present embodiment Al-Ti-B-Y-Ce fining agents and its preparation method and application are by following What step was realized:
(1)Raw material prepares, and prepares Al-Ti-B-Y-Ce fining agents and includes following mass percent component:Ti is that 5%, B is 1.2%, Y are that 0.2%, Ce is 0.3%, balance of Al;Aluminium powder, TiO are weighed on request2Powder, B2O3Powder, Al-Y alloys, Al-Ce are closed Gold, aluminium ingot, it is desirable to nAl powder: nTiO2Powder: nB2O3Powder=6:2:1, aluminium ingot purity 99. 9%;
(2)By aluminium powder, TiO2Powder and B2O3Powder, it is put into vacuum ball grinder, by ratio of grinding media to material 7:1, the high energy ball under rotating speed 300rpm Mill 7h, well mixed powder is placed in mould, is pressed into block;
(3)Aluminium ingot is put into the resistance furnace that power is 10kW, is heated to being completely melt, melt temperature is controlled at 800 DEG C -900 DEG C, cover one layer of ice crystal coverture, graphite bell jar press-in step(2)Block, graphite rod uniform stirring, react l5min;Instead After the completion of answering, 730 DEG C ~ 750 DEG C are cooled to;Graphite bell jar is pressed into Al-Ce, Al-Y intermediate alloy, 10min is stood, until middle Alloy is completely melt and spreads uniform;Press-in C2Cl6, refine, skim, aluminum melt is poured into warmed-up 200 DEG C of swage In, obtain Al-5Ti-1.2B-0.2Y-0.3Ce modifying-refining agents.
Thinning effect compares:
The condition of crystal grain refinement treatment is carried out to AlSi9Cu1 aluminium alloys:It is the graphite crucible resistance furnace melting of 10kW to use power AlSi9Cu1 aluminium alloys, after alloy is completely melt, cool the temperature to 750 DEG C, are incubated l0min, skim.Treat that melt temperature is down to At 730 DEG C, the Al-5Ti-1.2B-0.2Y-0.3Ce fining agents of 0.1wt% are added, stand 10min, skimmed, finally pour melt In the copper mould of 200 DEG C of injection preheating.The AlSi9Cu1 aluminium alloys of gained Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerates with The AlSi9Cu1 aluminium alloys of non-fine degenerate carry out the comparing of microstructure and mechanical property.
The Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerate AlSi9Cu1 aluminium alloy tensile strength that present embodiment is obtained 268MPa is reached, 22.9%, this embodiment party are improve than not carrying out the tensile strength 218MPa of AlSi9Cu1 alloys of fine degenerate The elongation percentage of the Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerate AlSi9Cu1 aluminium alloys that formula is obtained is thinner than not carrying out up to 6.1% The elongation percentage 3.7% for changing rotten AlSi9Cu1 alloys improves 64.8%.
The light microscopic of the Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerate AlSi9Cu1 aluminium alloys that present embodiment is obtained is such as Shown in Fig. 1.As seen from Figure 1, α-Al crystal grain is tiny, and alloy structure is uniform.
The Al-5Ti-1.2B-0.2Y-0.3Ce fine degenerate AlSi9Cu1 Aluminum alloy tensiles stress that present embodiment is obtained- The tensile stress-strain curve comparison diagram of the AlSi9Cu1 alloys of strain curve and non-fine degenerate is as shown in Figure 2.

Claims (7)

1. a kind of cast aluminium alloy gold Al-Ti-B-Y-Ce fining agents and its preparation method and application, it is characterised in that described Fining modifier includes following mass percent component:Ti is that 3.5% ~ 5.5%, B is that 0.5% ~ 1.5%, Y is 0.05% ~ 0.25%, Ce is 0.1% ~ 0.3%, balance of Al.
2. a kind of cast aluminium alloy gold according to claim 1 is with Al-Ti-B-Y-Ce fining agents and preparation method thereof and answers With, it is characterised in that Ti, B are with TiO2Powder, B2O3Powder is added, and Y, Ce are added in intermediate alloy form, using fusant reaction legal system Standby, specific method is as follows:
(1)Raw material prepares, and aluminium powder, TiO are weighed on request2Powder, B2O3Powder, Al-Y alloys, Al-Ce alloys, aluminium ingot, it is desirable to nAl powder : nTiO2Powder: nB2O3Powder=6:(1.5~2.5):(1.2~1.5), aluminium ingot purity 99. 9%;
(2)By aluminium powder, TiO2Powder and B2O3Powder, be put into vacuum ball grinder, by certain ratio of grinding media to material under certain rotating speed high energy Ball milling for a period of time, well mixed powder is placed in mould, is pressed into block;
(3)Aluminium ingot is put into the resistance furnace that power is 10kW, is heated to being completely melt, melt temperature is controlled at 800 DEG C -900 DEG C, cover one layer of ice crystal coverture, graphite bell jar press-in step(2)Block, graphite rod uniform stirring, react 15min;Instead After the completion of answering, 730 DEG C ~ 750 DEG C are cooled to;Graphite bell jar is pressed into Al-Ce, Al-Y intermediate alloy, 10min is stood, until middle Alloy is completely melt and spreads uniform;Press-in C2Cl6, refine, skim, aluminum melt is poured into warmed-up 200 DEG C of swage In, obtain Al-Ti-B-Y-Ce modifying-refining agents.
3. method according to claim 2, it is characterised in that step(2)Described certain ratio of grinding media to material is(7~10):1.
4. method according to claim 2, it is characterised in that step(2)Described certain rotating speed is 250 ~ 400rpm.
5. method according to claim 2, it is characterised in that step(2)Described a period of time is 6 ~ 8h.
6. method according to claim 2, it is characterised in that aluminium powder is 200 mesh, TiO2Powder is 300 mesh, B2O3Powder is 325 mesh.
7. a kind of method according to claim 2, it is characterised in that cast aluminium alloy gold Al-Ti-B-Y-Ce fining agents of preparation AlSi9Cu1 cast aluminium alloy golds are applied to, and are compared with the AlSi9Cu1 cast aluminium alloy capabilities of non-fine degenerate, refined AlSi9Cu1 intensity is lifted to 268MPa by 218MPa after rotten, improves 22.9%;Elongation percentage, to 6.1%, is carried by 3.7% lifting Rise 64.8%.
CN201611183562.XA 2016-12-20 2016-12-20 A kind of cast aluminium alloy gold Al Ti B Y Ce fining agents and its preparation method and application Pending CN106756276A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107354324A (en) * 2017-06-30 2017-11-17 宁夏大学 Rare earth optimizes the method and modified alloy of pack alloy
CN108103363A (en) * 2017-12-11 2018-06-01 南昌大学 It is a kind of for refinement-alterant of hypoeutectic silumin alloy and its preparation method and application
CN108277374A (en) * 2018-02-09 2018-07-13 兰州理工大学 A kind of Al-Ti-C-Y composite crystal grain fining agents, alloy and preparation method thereof
CN109811161A (en) * 2019-02-27 2019-05-28 北京工业大学 A kind of large volume fraction nanoscale Al-TiB2Intermediate alloy and preparation method thereof
CN111485130A (en) * 2020-04-29 2020-08-04 江苏华企铝业科技股份有限公司 Al-RE-Y alloy refiner and continuous casting and rolling preparation method thereof
CN112404374A (en) * 2020-11-30 2021-02-26 中国科学院金属研究所 Preparation method and application of refiner

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CN102424923A (en) * 2011-11-29 2012-04-25 黄冈华尔铝合金有限公司 Al-Ti-B-rare earth(RE) grain refiner and preparation method thereof
CN102644010A (en) * 2012-04-11 2012-08-22 北京工业大学 Al-Ti-B-Er refiner and preparation method thereof

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JPH10317083A (en) * 1997-05-13 1998-12-02 Kobe Steel Ltd Grain refiner for aluminum alloy
CN1485451A (en) * 2002-09-28 2004-03-31 东南大学 Composite grain refiner for aluminium, aluminum alloy and preparing process therefor
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107354324A (en) * 2017-06-30 2017-11-17 宁夏大学 Rare earth optimizes the method and modified alloy of pack alloy
CN108103363A (en) * 2017-12-11 2018-06-01 南昌大学 It is a kind of for refinement-alterant of hypoeutectic silumin alloy and its preparation method and application
CN108103363B (en) * 2017-12-11 2019-10-29 南昌大学 A kind of refinement-alterant and its preparation method and application for hypoeutectic silumin alloy
CN108277374A (en) * 2018-02-09 2018-07-13 兰州理工大学 A kind of Al-Ti-C-Y composite crystal grain fining agents, alloy and preparation method thereof
CN109811161A (en) * 2019-02-27 2019-05-28 北京工业大学 A kind of large volume fraction nanoscale Al-TiB2Intermediate alloy and preparation method thereof
CN111485130A (en) * 2020-04-29 2020-08-04 江苏华企铝业科技股份有限公司 Al-RE-Y alloy refiner and continuous casting and rolling preparation method thereof
CN112404374A (en) * 2020-11-30 2021-02-26 中国科学院金属研究所 Preparation method and application of refiner

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