CN1298878C - Aluminum silicon alloy series possessing granulated silicon phase and its process - Google Patents
Aluminum silicon alloy series possessing granulated silicon phase and its process Download PDFInfo
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Abstract
The present invention relates to an aluminum-silicon alloy series with a granular silicon phase and a technical method thereof, which is characterized in that (1) the aluminum-silicon alloy series comprises the chemical constituents (wt%): 11.5 to 17.0% of Si, 0.5 to 5.0% of Cu, 0.2 to 1.5% of Mg, 0.5 to 3.0% of Ni, 0.1 to 0.9% of Mn, less than 1.0% of Zn, less than 1.3% of Fe, 0.02 to 0.30% of Ti and Al as the rest; (2) a cast metallic-phase structure is composed of modified or less-modified aluminum-silicon eutectic crystal and dendritic-crystal primary aluminum; (3)a heat-treated metallic-phase structure is composed of an aluminum basal body and granular silicon uniformly distributed. The technology is characterized in that electrolytic aluminum-silicon alloy and aluminum-silicon master alloy are melted and then are heated to 150 DEG C above a liquidus line for degassing refining; Al-Sr master alloy, Al-RE master alloy or sodium salt is added or is not added to the melt, and then the melt is agitated uniformly, is made to stand for 15 minutes and then is cast to form casts. The amount of an added modifier of the present invention is from 0.01 to 0.10 wt% and is far lower than the value of 0.1 to 0.4 wt%, which is reported in literature so as to avoid the generation of shrinkage porosity and guarantee to obtain sound castings. The present invention is suitable for light-weight aluminum-silicon alloy castings with the high requirements of abrasion resistance.
Description
Technical field
The present invention relates to a kind of aluminium silicon alloy series and preparation method thereof with granular silicon phase.(silicone content＜12% usually) adds or does not add the aluminum silicon alloy that aluminium silicon master alloy constitutes the Different Silicon amount in the electrolytic aluminum silicon alloy more precisely, add a small amount of strontium or rare earth or the agent of sodium salt iso-metamorphism or the processing of not going bad again, can obtain fully by going bad or owing the aluminum silicon alloy that rotten eutectic is formed.Be the granular silicon phase through these silicon inversion of phasess of solution treatment again.
Background technology
Aluminum silicon alloy is a kind of lightweight metal material, has high specific tenacity and wear resisting property.Be further enhanced along with the silicon amount increases the alloy wear-resisting performance, but primary silicon thick, that corner angle are arranged separates out thereupon, worsened alloy mechanical performance and processing characteristics.Refinement or group, nodularization primary silicon mutually or restrain separating out of it and make it to have eutectic structure all can improve alloy toughness, intensity and processing characteristics significantly.
Usually add phosphorus base silicon phase fining agent refinement silicon phase effectively in eutectic or transcocrystallized Al-Si alloy, but can not change their original forms, promptly primary silicon is cerioid, and Eutectic Silicon in Al-Si Cast Alloys still is pin, sheet, has influence on the improvement of alloy property.The alloy of silicon phase nodulizing agent that adds phosphorous, titanium, boron, rare earth etc. through T6 thermal treatment after, Eutectic Silicon in Al-Si Cast Alloys and primary silicon obtain, nodularization, thereby the mechanical property and processing characteristics (the Hsien-Yang Yeh of hypereutectic alloy have been improved greatly, Ru-Yao Wang et al USP6,261,391 B1 Jul.17,2001) but, this technology is rolled into a ball in carrying out the T6 heat treatment process, spherical primary silicon phase size is difficult to less than 15-20 μ m, sometimes group, spherical primary silicon are assembled bunchiness, size is bigger, influences alloy property.(Si＜15%) excessive Na of adding or Sr (0.1-0.4%) and Ti, Cr, Mo, Ta, elements such as Tl, V in transcocrystallized Al-Si alloy, can form intermetallic compound, the external nucleus that can serve as primary silicon, promote the primary silicon refinement, and make Eutectic Silicon in Al-Si Cast Alloys rotten or restrain separating out of primary silicon, obtain eutectic structure completely.But cause shrinkage porosite easily because Na or Sr add-on are too high, be difficult to obtain sound casting (Rogers K et al USP 5,484,492 Jan.16,1996).The hyperthermia and superheating treatment process that the eighties occurs later on can improve alloy property greatly.Its technology characteristics is earlier alloy superheat to be arrived 1100-1200 ℃.Various impurity and siliceous point all were dissolved in and formed homogeneous aluminium silicon melt in the aluminium liquid this moment.Add superfine Ti N or AlN again and form a large amount of external nucleus and make primary silicon and Eutectic Silicon in Al-Si Cast Alloys obtain abundant refinement, thereby improve alloy use properties (Shepelov.L et al USP6,132,532 Oct.17 2000) greatly.Overheated-fast cold technology (or being referred to as the processing of heat speed) appears again in recent years.For example, the Al-18%Si hypereutectic alloy is heated to 950 ℃, be heated to 750 ℃ same alloy melt with another group then and mix, cast again can be refined to primary silicon (heavily fortified point increases fortune poplar root storehouse Zhou Yao and China YouSe Acta Metallurgica Sinica 1995 (4) 133-135) below the 20 μ m.Yet these hyperthermia and superheatings are handled to production and are brought many technologic difficulties, are difficult to apply.The electrolytic aluminum silicon alloy bears 920-950 ℃ of high temperature and current processing in process of production, also can obtain the effect of pyroprocessing when solidifying, bigger condensate depression and tiny rotten Eutectic Silicon in Al-Si Cast Alloys and more dendritic crystal state primary aluminium (Ru-Yao Wang Wei-Hua Lu L Hogan:Materials Science and EngineeringA348 (2003) 289-298) mutually promptly occur.This moment, electrolytic aluminum silicon alloy eutectic point silicon phase composition moved to about 16%.So, can guess siliceous electrolysis hypereutectic alloy below 16% and will have eutectic structure, and should be in status degenerativus.And a small amount of small size primary silicon phase only appears in siliceous alloy below 18%.Unstable on this microstructure thermodynamics, be transformed into stabilizing tissue during heating, obtain to be evenly distributed on the particulate Si phase on the aluminum substrate.
Summary of the invention
Based on above-mentioned cognition, the object of the present invention is to provide a kind of aluminium silicon alloy series and preparation method thereof to provide simple and easy, a cheap new way for automobile, the aviation part of producing lightweight aluminium silicon alloy high-abrasive material with granular silicon phase.
Purpose of the present invention realizes in the following manner:
Described aluminium silicon alloy series contains Si 12.0-17.0% (weight, down together), Cu 0.5-5.5%, Mg0.2-1.5%, Ni 0.25-3.0%, Mn 0.01-0.9%, Zn＜1.0%, Fe＜1.3%, Ti 0.02-0.30%, and surplus is Al.
The furnace charge that aluminum silicon alloy processing method of the present invention is used comprises electrolytic aluminum silicon alloy (the Si amount is in the 6.0-12.0% scope usually), aluminium silicon master alloy and other Al-X master alloy (X refers to other element of described alloy).Melt with resistance furnace or other smelting furnace such as reverberatory furnace.Be warmed up to above 150 ℃ of liquidus line, the refining of degassing adds strontium or rare earth alterative then or adds two kinds of rotten drug simultaneously or the sodium salt or the processing of not going bad.Jiao mixes evenly, leave standstill again 15 minutes promptly pourable.Primary silicon does not appear in the alloy casting state tissue, and by rotten or owe rotten eutectic and the dendritic crystal state primary aluminium is formed.Surpass 1.5 hours the duration of pouring and slight rotten decline occurs.Occur rotten decline after the remelting, but still keep eutectic structure.
Strontium of the present invention or rare earth use Al-10%Sr or Al-10%RE (RE is rare earth element) master alloy or sodium salt respectively, and add-on is all in the 0.01-0.10wt% scope.The The combined add-on is also in the 0.01-0.10wt% scope.Use the rotten effect of sodium salt or rare earth not as strontium.
Aluminum silicon alloy of the present invention is with the refining of degassing of nitrogen or hexachloroethane.
Aluminum silicon alloy of the present invention is through after the solution treatment, and the rotten or silicon of owing to go bad changes the granular silicon phase mutually into, is evenly distributed on the aluminum substrate.
Advantage of the present invention is:
(1) aluminum silicon alloy of the present invention has granular silicon and is meant mutually in the electrolytic aluminum silicon alloy and adds aluminium silicon master alloy, be adjusted under eutectic or the transcocrystallized Al-Si alloy prerequisite, add a small amount of strontium or rare earth or sodium salt degeneration drug or the processing of not going bad, utilize electrolytic aluminum silicon alloy inherent just can restrain separating out of primary silicon again, and formation is gone bad or owe the THE MODIFIED ALUMINIUM-SILICON EUTECTIC tissue from rotten performance.Pass through solution treatment again, just can obtain the particulate Si phase, be evenly distributed on the aluminum substrate.
(2) the present invention selects the electrolytic aluminum silicon alloy for use, has avoided the technologic difficulty that hyperthermia and superheating brought, and but has hyperthermia and superheating and handles the rotten effect of eutectic structure that is produced.
(3) the present invention utilizes unsettled characteristic on this microstructure thermodynamics, by make it decomposition at 480-510 ℃ of scope internal heating, obtains the granular silicon phase, is evenly distributed on the aluminum substrate, and the phenomenon that the silicon grain is assembled bunchiness do not occur.
(4) quantity of added strontium of the present invention or rare earth all is worth far below the essential of bibliographical information (Rogers K et alUSP 5,484,492 Jan.16,1996).This has just been avoided the generation of shrinkage porosite, guarantees to obtain fine and close foundry goods.The silicon of alloy is particulate state mutually, and most of size is about 5 μ m.
(5) the invention belongs to the aluminium alloy in-situ composite, be applicable to production requirement is in light weight, wear resistance is high zero, parts.
Description of drawings
Fig. 1 electrolysis aluminium-silicon ingots as-cast structure (100X).Chemical Composition is: Si 12.12%, Cu 0.88%, Mg 0.91%, Mn 0.01%, Ni 0.81%, Fe 0.25%, Ti 0.09%, Sr＜0.0006%.It is rotten fibrous that Eutectic Silicon in Al-Si Cast Alloys is, large dendritic crystal shape primary aluminium uniform distribution.Occur on the eutectic crystal boundary a small amount of sheet silicon mutually with fritter shape primary aluminium mutually.
Fig. 2 electrolysis cocrystallized Al-Si alloy heat treatment state tissue (SEM photo).The same Fig. 1 of Chemical Composition.Eutectic Silicon in Al-Si Cast Alloys is particulate state, and most of sizes are less than 5 μ m.Overall dimension is no more than 10 μ m.Do not find the primary silicon phase.The nodularization characteristic that electrolytic aluminum silicon alloy silicon phase is described shows in the time of 500 ℃.
The heat treatment state tissue (100X) that the remelting of Fig. 3 Fig. 1 cocrystallized Al-Si alloy is 3 times.Dendroid primary aluminium uniform distribution.Eutectic Silicon in Al-Si Cast Alloys still is particulate state, is distributed in the primary aluminium interdendritic, and Shao Xu Long is big, and most of sizes are about 10 μ m.
Fig. 4 transcocrystallized Al-Si alloy heat treatment state tissue (100X).Chemical Composition is: Si 13.7%, Cu 0.98%, Mg 0.55%, Mn 0.49%, Ni 0.30%, Fe 0.26%, Ti 0.08%, Sr＜0.0006%.Solid solution temperature 495-505 ℃.Silicon is evenly distributed on the aluminum substrate mutually in pelletized form, and most of sizes are less than 5 μ m.Some larger-size silicon phases of eutectic circumferential distribution.
Fig. 5 transcocrystallized Al-Si alloy as-cast structure (100X).Chemical Composition is: Si 15.7%Cu 1.00%, Mg 0.55%, Mn 0.50%, Ni 0.28%, Fe 0.33%, Ti 0.09%, Sr 0.0051%.Before the alloy cast, add the processing of going bad of Al-10%Sr master alloy.Micro-metallographic structure is by being chrysanthemum shape al-si eutectic body and primary aluminium phase composite.Eutectic Silicon in Al-Si Cast Alloys is modification state mutually, and is tiny unusually.A small amount of short-movie shape silicon phase appears on the eutectic periphery primary aluminium matrix.Illustrate that strontium has played metamorphism, restrain separating out of primary silicon.
The metallographic structure of Fig. 6 Fig. 5 transcocrystallized Al-Si alloy heat treatment state.Solid solution temperature is 495-505 ℃.Silicon is particulate state mutually, and size is very tiny, and is most of less than 5 μ m.Some sheet silicon phases appear in the eutectic periphery.
Fig. 7 transcocrystallized Al-Si alloy heat treatment state metallographic structure (100X).Chemical Composition is: Si 14.2%, Cu 1.05%, Mg 0.50%, Mn 0.36%, Ni 0.28%, Fe 0.30%, Ti 0.08%.Before the alloy cast, add the processing of going bad of Al-10%RE master alloy.Eutectic Silicon in Al-Si Cast Alloys is mutually owes status degenerativus.Dendritic crystal state primary aluminium phase amount is more, is evenly distributed.A small amount of small size primary silicon appears.After solution treatment (Heating temperature is 495-505 ℃), Eutectic Silicon in Al-Si Cast Alloys disconnects mutually on a small quantity, is transformed into granularly, and most of form does not change.Illustrate a little less than the rare earth alloy metamorphism is than strontium manyly, 500 ℃ of following silicon are difficult to nodularization mutually.
Embodiment
Further set forth substantive distinguishing features of the present invention and obvious improvement below by specific embodiment.But the present invention only is confined to embodiment by no means.
Embodiment 1
Electrolysis cocrystallized Al-Si alloy ingot Chemical Composition is: Si 12.12%, Cu 0.88%, Mg 0.91%, Mn 0.01%, Ni 0.81%, Fe 0.25%, Ti 0.09%, Sr＜0.0006%.Melt with resistance furnace.Be warming up to 720 ℃, degas with nitrogen.Do not add any alterant.。Be incubated after 15 minutes, pour into and be preheated to 300 ℃ metal mold.Specimen size is 45 * 50 * 120mm.In the alloy casting state metallographic structure, the primary silicon phase do not occur, the al-si eutectic body is main the composition with a fairly large number of dendritic crystal state primary aluminium mutually.Silicon is modification state mutually, unusual tiny and distortion (see figure 1).After 6 hours, silicon is transformed into particulate state mutually through 500 ℃ of solution treatment, is evenly distributed on the aluminum substrate, and most of sizes are less than 5 μ m.(see figure 2).
Embodiment 2
Electrolysis cocrystallized Al-Si alloy ingot.Chemical Composition and melting process are with example 1.Remelting 3 times.After 6 hours, silicon is transformed into particulate state mutually through 500 ℃ of solution treatment, is evenly distributed on the aluminum substrate, and size slightly increases, and majority is still less than 10 μ m (see figure 3)s.The nodularization character that electrolytic aluminum silicon alloy silicon phase is described increases and weakens gradually along with the remelting number of times.
Embodiment 3
Transcocrystallized Al-Si alloy Chemical Composition Si 13.7%, Cu 0.98%, Mg 0.55%, Mn 0.49%, Ni 0.30%, Fe 0.26%, Ti 0.08%, Sr＜0.0006%.Charge composition comprises electrolytic aluminum silicon alloy (seeing that Fig. 1 illustrates), Al-25%Si master alloy.Melt with resistance furnace.Be warming up to 720 ℃, degas with nitrogen.Do not add any alterant.Be incubated after 15 minutes, pour into and be preheated to 300 ℃ metal mold.Specimen size is 45 * 50 * 120mm.In the alloy casting state metallographic structure, the primary silicon phase do not occur, the al-si eutectic body is main the composition with a fairly large number of dendritic crystal state primary aluminium mutually.Silicon is modification state mutually, unusual tiny and distortion.After 6 hours, silicon is transformed into particulate state mutually through 500 ℃ of solution treatment, is evenly distributed on the aluminum substrate, and most of sizes are less than 5 μ m.Some larger-size silicon phase (see figure 4)s of eutectic circumferential distribution.Illustrate that the electrolytic aluminum silicon alloy adds small amount of aluminum silicon master alloy, even if do not go bad processing, also can keep the characteristic of silicon phase nodularization.
Embodiment 4
The transcocrystallized Al-Si alloy Chemical Composition is Si 15,7%, Cu 1.00%, Mg 0.55%, Mn 0.50%, Fe 0.33%, Ni 0.28%, Ti 0.09%, Sr 0.0051%.Charge composition and melting process are with example 3.The back of degassing adds Al-10%Sr master alloy (0.1%) processing of going bad.Jiao mixes evenly, leaves standstill cast after 15 minutes again.Sample is with example 1.The alloy casting state metallographic structure is made up of the al-si eutectic body basically, and each eutectic is surrounded mutually by aluminium.The silicon at eutectic center obtains fully rotten mutually, and is very tiny, is distributed in (see figure 5) on the aluminum substrate but the silicon on the crystal boundary is corynebacterium mutually in the radiating mode.The aluminium phase amount is than greatly increasing without the rotten alloy of handling (example 3) of strontium.Must go bad when the alloy silicon content is described near non-equilibrium eutecticum composition 16%, otherwise silicon is rotten insufficient mutually.After 6 hours, silicon is transformed into particulate state mutually through 500 ℃ of solution treatment, is evenly distributed on the aluminum substrate, and most of sizes are less than 5 μ m.Some larger-size silicon phase (see figure 6)s of eutectic circumferential distribution.The transcocrystallized Al-Si alloy that explanation is made up of the electrolytic aluminum silicon alloy still can keep the nodularization characteristic of silicon phase after rotten the processing.In addition, present embodiment has slight silicon hydro-planing.
Embodiment 5
Transcocrystallized Al-Si alloy Chemical Composition, charge composition and melting process are with example 3.The back of degassing adds the processing of going bad of 0.1% Al-10%RE master alloy.Jiao mixes evenly, leaves standstill cast after 15 minutes again.Sample is with example 1.After 6 hours (Heating temperature is 495-505 ℃), Eutectic Silicon in Al-Si Cast Alloys disconnects mutually on a small quantity, is transformed into granular through solution treatment.Most of form (see figure 7) that do not change.Illustrate a little less than the rare earth alloy metamorphism is than strontium manyly, 500 ℃ of following silicon are difficult to nodularization mutually.
Claims (5)
1. aluminum silicon alloy with granular silicon phase is characterized in that:
(1) Chemical Composition is: Si 12.0-17.0, Cu 0.5-5.5, Mg 0.2-1.5, Ni 0.5-3.0, Mn0.1-0.9, Zn＜1.0, Fe＜1.3, Ti 0.02-0.30, and surplus is Al, more than is weight percentage;
(2) as-cast metallographic structure is by rotten or owe the THE MODIFIED ALUMINIUM-SILICON EUTECTIC body and the dendritic crystal state primary aluminium is formed;
(3) after the thermal treatment metallographic structure by aluminum substrate and equally distributed granular silicon phase composite.
2. prepare the method with aluminum silicon alloy of granular silicon phase as claimed in claim 1, it is characterized in that adopting in following two kinds of methods any one to prepare:
(1) (a) used furnace charge is electrolytic aluminum silicon alloy, aluminium silicon master alloy, foundry returns, the alloy composition is: Si 12.0-17.0, Cu 0.5-5.5, Mg 0.2-1.5, Ni 0.5-3.0, Mn 0.1-0.9, Zn＜1.0, Fe＜1.3, Ti 0.02-0.30, surplus is Al, more than is weight percentage;
(b) with resistance furnace or reverberatory furnace melting batch, charge-temperature rises to above 150 ℃ of alloy liquid phase line, the refining of degassing;
(c) melt is with strontium or rare earth alloy, or adds strontium and rare earth alloy simultaneously, or adds the sodium salt processing of go bad, and add-on is 0.01-0.10wt%, and Jiao mixes evenly, leaves standstill after 15 minutes to pour into a mould;
(d) heat-treat then, solid solution temperature is 480-520 ℃, heats 6-8 hour, and alloy the granular silicon phase occurs and is evenly distributed in the aluminum substrate;
(2) (a) used furnace charge is electrolytic aluminum silicon alloy, aluminium silicon master alloy, foundry returns, the alloy composition is: Si 12.0-17.0, Cu 0.5-5.5, Mg 0.2-1.5, Ni 0.5-3.0, Mn0.1-0.9, Zn＜1.0, Fe＜1.3, Ti 0.02-0.30, surplus is Al, more than is weight percentage;
(b) with resistance furnace or reverberatory furnace melting batch, charge-temperature rises to above 150 ℃ of alloy liquid phase line, the refining of degassing,
(c) heat-treat then, solid solution temperature is 480-520 ℃, heats 6-8 hour, and alloy the granular silicon phase occurs and is evenly distributed in the aluminum substrate.
3. by the described preparation method of claim 2, it is characterized in that described strontium and rare earth add with the master alloy form with aluminum silicon alloy of granular silicon phase.
4. by the described preparation method with aluminum silicon alloy of granular silicon phase of claim 3, the master alloy that it is characterized in that described strontium and rare earth is Al-10%Sr or Al-10%RE, and RE is a rare earth element.
5. by the described preparation method of claim 2, it is characterized in that described refining employing nitrogen or the hexachloroethane of degassing with aluminum silicon alloy of granular silicon phase.
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| CN1120598A (en) * | 1994-10-12 | 1996-04-17 | 东北轻合金加工厂 | Modification method of High silicon-aluminum alloy |
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