CN1521283A - Aluminium silicon alloy series silicon, iron biphase agglomerating agent and agglomerating method therefor - Google Patents

Abstract

The present invention relates to one kind Si-Fe double-phase pelletizing agent for Si-Al alloy series and its pelletizing method. The Si-Fe double-phase pelletizing agent is MoS2 and/or MnS2 with the added amount being 0.1-0.8 wt%, or is one of P, Sr and Sb in the added amount of 0.01-0.10 wt% and MoS2 and/or MnS2 in the added amount of 0.1-0.8 wt%. The pelletizing treatment process includes smelting Si-Al alloy, raising the temperature to 150 deg.c over the liquid phase line, deairing to refine, adding the pelletizing agent via stirring, letting stand for 15 min and casting. The heat treatment includes solid solution treatment and ageing treatment. The present invention is suitable for aluminum casting requiring high antiwear property and Al-Si alloy with smelted waste material.

Description

Aluminium silicon alloy series silicon, iron two-phase agglomerating agent and groupization method thereof

Technical field:

The present invention relates to aluminium silicon alloy series silicon, iron two-phase agglomerating agent-sulfide, aluminium silicon alloy series is handled through P, Sb or Sr earlier more precisely, adds MnS and or MoS again ₂Can eliminate thick needle-like iron phase, obtain plum blossom shape or group, granular iron phase, again after solution treatment, can obtain corynebacterium, a shape Eutectic Silicon in Al-Si Cast Alloys mutually with tiny primary silicon mutually, thereby the intensity of alloy and plasticity are improved.

Background technology:

The cast Al-Si alloy performance depends on the form of second phase to a great extent.Undressed alloy, when speed of cooling is hanged down (as sand mold casting), silicon occurs with thick pin, lamellar morphology.Alloy uses foundry returns too much, and iron-holder increases (example is for reaching 0.6%), and thick needle-like iron phase is easy to separate out.These thick pins, sheet second mutual-assistance alloy embrittlement, processing difficulties.These tissues of refinement or change their form, for example silicon becomes the fiber fines shape mutually, and iron phase becomes Chinese character shape or plum blossom shape or a shape all can improve alloy strength, plasticity and processing characteristics.If they all with, granular form occurs, alloy strength and plasticity can also further be improved, and have good wear resistance.Usually can adopt and add their form of alterant change.For example, adding Na, Sr or rare earth element (RE) can make silicon separate out with fibrous form.Adding P or Sb can the refinement pin, lamellar morphology silicon phase.Unite and add P, Ti, B, Zr can make with RE that silicon is rolled into a ball mutually, nodularization.(261,390, B1, Jul 17,2001 for Hsien-Yang Yeh, Ru-yao Wang et al USP6) strict control foundry goods speed of cooling can make also with the temperature field that silicon is rolled into a ball mutually, nodularization.May change the iron phase form but above-mentioned treatment process is neither.Add one or more transition elements V, Cr Mn, Co, Ni, Mo and rare earth element can change the form that exists of iron phase, but very little for the influence of silicon phase morphology.Have only element sulphur to have certain metamorphism (Zhu Hanliang, merchant's equalization, " additive and element sulphur are to the influence of iron phase form in the zl108 alloy ", Special Processes of Metal Castings and non-ferrous alloy simultaneously to silicon phase and iron phase, 1996 the 4th phases, but contaminate environment should not separately or be united employing the 5-7 page or leaf).In addition, with insulation more than the alloy superheat to 1100 ℃, add TiN or AIN ultrafine powder (being of a size of 10-80nm) again or also can make iron phase become Chinese character shape and bulk with ultrasonication again, and obtain tiny eutectic structure (ShepelovLet al USP on October 17th, 6132532,2000).

Summary of the invention:

At present, useless both at home and abroad, old aluminum alloy part is increasing.Use foundry returns must cause that the alloy iron amount increases.How to accomplish to make simultaneously silicon phase and iron phase group, granulation just to become metallurgical in the world, casting industry problem very deeply concerned.The present invention relates to a kind of silicon, iron two-phase agglomerating agent, make simultaneously in the aluminum silicon alloy silicon mutually and iron phase group, granulation, and the intensity and the plasticity of raising alloy.This just provides a kind of simple and easy, cheap new way for waste and old parts of reuse and smear metal in a large number, reduction product cost, raising casting quality.

The objective of the invention is to implement by following manner:

Described aluminium silicon alloy series is to contain Si6.0-20.0% (weight, down together), Cu0.5-5.0%, and Mg 0.2-1.5%, Ni 0.5-3.0%, Mn0.1-0.9%, Zn5.5-13%, Fe＜1.3%, surplus is Al.

Described aluminum silicon alloy melts with resistance furnace.Be warming up to above 150 ℃ of liquidus line, the refining of degassing can add a kind of and MoS among P or Sr or the Sb ₂And/or MnS, also can not add among three kinds of P or Sr or the Sb any, and only add MoS ₂And/or MnS.Stir, leave standstill 15 minutes after, promptly pourable.Iron phase changes plum blossom shape, short strip shape or group, granular into by thick pin, sheet in the cast alloy, is evenly distributed on the matrix, and silicon phase or refinement or rotten are decided on adding P or Sb or Sr.Primary silicon also can obtain refinement.Alloy is through 510 ± 5 ℃ of heating after 4-6 hour, and Eutectic Silicon in Al-Si Cast Alloys changes into, granular, becomes corynebacterium on a small quantity.This alloy strength can return to or the approaching low former alloy level of iron, and has good unit elongation.Use the alloy of P or Sb, insulation, the duration of pouring surpass 4 hours, slight decline just occurs.After the remelting, do not have obvious decay, still keep the two-phase modification effect.When using Sr, can continue 1.0-1.5 hour the duration of pouring.After the remelting, decline appears in silicon mutually.

P of the present invention, Sr and Sb use the Cu-8%P alloy respectively, Al-10%Sr alloy and Al-10%Sb alloy, and add-on is 0.01-0.10%.Described sulfide M oS ₂The adding scope is 0.1-0.8%, and MnS adding scope is 0.1-0.8%, and the two mixes add-on is 0.1-0.8%.Used sulfide removes MnS and MoS ₂Outside, can also be nickelous sulfide, chromic sulfide or cobaltous sulfide, but the groupization effect be not as good as MoS ₂, MnS.

Aluminum silicon alloy N of the present invention ₂Gas or C ₂Cl ₆The refining treatment of degassing.

The two-phase agglomerating agent of aluminum silicon alloy of the present invention is meant that the adding at P or Sr or Sb makes under Si refinement or the rotten prerequisite, adds MoS again ₂And/or MnS makes ferrosilicon group mutually, or refers to only use MoS ₂, MnS or other transition element sulfide change iron phase and silicon phase morphology.

The selected MoS of the present invention ₂Or MnS or other sulfide is as silicon, iron phase agglomerating agent, avoided using elemental sulfur in the prior art and causes pollution to environment.Moly-sulfide and/or manganese sulfide are compounds stable in the sulfide, do not have the defective of elemental sulfur and also fairly obvious to group's effect of ferro element.The present invention is applicable to and requires that attrition resistant aluminium silicon foundry goods and fusing are a large amount of reclaims useless, old parts, and iron level is less than 1.3% aluminum silicon alloy.

Description of drawings:

Fig. 1 Sr becomes the ZL101 alloy microscopic structure.Add MoS ₂0.6% and T6 handle.Iron phase is changed agglomerating, granular by thick acicular structure before handling, become the bent-strip shape on a small quantity, is evenly distributed on the crystal boundary.Silicon still granulates mutually, is mingled with a small amount of corynebacterium, 250X.

Fig. 2 P becomes the ZL 109 alloy microstructure.Add MoS ₂0.3% and Mn S0.2%T6 handle.Iron phase is, granular, be strip on a small quantity.Silicon becomes breakaway-element bulk and corynebacterium, 200X mutually.

Fig. 3 P becomes the ZL 109 alloy microstructure.Add MoS ₂0.5%.720 ℃ are incubated 2 hours.T6 handles.With Fig. 2 alloy phase ratio, iron phase still is, granular, but group, granular silicon phase showed increased, 200X.

Fig. 4 remelting Fig. 2 P becomes the ZL 109 alloy microstructure.High temperature (720 ℃) stopped 2 hours.T6 handles.Iron phase still is, granular, a small amount of strip.Silicon some decline mutually, corynebacterium silicon phase amount increases 200X.

The industrial P of Fig. 5 becomes ZL108 piston alloy microstructure.Add MoS ₂0.3%.750 ℃ are incubated 2 hours and the T6 processing.Iron phase is the plum blossom shape, and a shape is evenly distributed on the matrix.Silicon is tiny corynebacterium mutually, and 0.3%MoS is described ₂Be not enough to guarantee the group's of acquisition granular silicon phase, 100X.

Fig. 6 Sb becomes the ZL 109 alloy microstructure.Add MoS ₂0.5%.T6 handles.Silicon, iron phase are a shape form, are distributed in α-Al interdendritic, 250X.

Fig. 7 becomes ZL 109 alloy SEM microstructure for Fig. 6 Sb, and silicon is the three-dimensional pattern of spherulitic mutually.

Fig. 8 is without MoS ₂The ZL401 alloy microscopic structure of handling.Add MoS ₂0.3%, only carry out natural aging.Silicon, iron phase are thick needle-like, and primary dendrite aluminium is very thick mutually, 125X.

Fig. 9 MoS ₂The ZL401 alloy microscopic structure of handling.Add MoS ₂0.3%, only carry out natural aging.Iron phase is corynebacterium, and part is the hour hand shape, reaches design requirements.Silicon is short strip shape mutually, and part is rotten.Primary aluminium phase secondary dendrite arm spacing obviously reduces 125X.

Embodiment:

Below by specific embodiment, further set forth substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to embodiment by no means.

Embodiment 1

Sr becomes the ZL101Al-Si alloy composition and is Si6.7%, Mg0.25%, and Mn0.30%, Fe0.85%, the Sr add-on is 0.01%.Melt with resistance furnace.Molten clear, be warming up to 700 ℃ and degas with nitrogen.Add Al-10%Sr master alloy and 0.6%MoS ₂, stir.720 ℃ of insulations poured into and are preheated to 300 ℃ metal mold after 15 minutes.Specimen size is 40 * 50 * 120mm, and thermal treatment process comprises solution treatment (510 ± 5 ℃, 5 hours, shrend) and ageing treatment (210 ℃ ± 5 ℃, 8 hours, air cooling).Iron phase changes agglomerating, granular and a small amount of short strip shape by thick needle-like in the alloy casting state metallographic structure, is distributed in (see figure 1) on the crystal boundary.The iron phase form does not have considerable change after the thermal treatment.Silicon occurs with tiny granular form, is mingled with a small amount of corynebacterium tissue.

Table 1 is listed and is added MoS ₂Sr become ZL101Al-Si alloy casting state and heat treatment state microstructure, MoS ₂Add-on be 0.6%.

Table 1:Sr becomes ZL101 alloy microscopic structure (MoS ₂Add-on 0.6%)

	The silicon phase	Iron phase	Nascent Al phase
				As cast condition	Tiny, fibrous	Granular, corynebacterium	The refinement of secondary spacing
Heat treatment state	Granular, corynebacterium	Granular, corynebacterium	Dendrite quantity increases

Embodiment 2:

P become the ZL 109 alloy chemical ingredients into: Si 11.68%, and Mg 0.76%, Cu1.01%, Ni0.80%, Mn 0.19%, Ti＜0.04%, Fe 0.80%.Fusing, cast and thermal treatment process are with embodiment 1.Add the Cu-8%P alloy earlier.Add MoS again ₂And MnS, add-on is respectively 0.3% and 0.2%.Table 2 is enumerated the microstructure of as cast condition, insulation two hours and remelting ZL 109 alloy.

Table 2:P becomes ZL 109 alloy through MoS ₂With the metallographic structure after the MnS processing

Alloy state	The silicon phase	Iron phase	The primary aluminium phase	Remarks
					As cast condition	Tiny faller gill shape	The granule shape	A small amount of dendrite	Topped dose of available sylvite or sodium salt
Heat treatment state	The granule shape	The granule shape
			As cast condition (being incubated 2 hours)	Tiny sheet corynebacterium	The granule shape	The decline of silicon phase spheroidization is not obvious
Heat treatment state (being incubated 2 hours)	Granule shape, corynebacterium	The granule shape
			Remelting, heat treatment state	Granule shape, corynebacterium	Granule shape, strip		The two-phase metamorphism is slightly failed

P-MoS ₂The compound agglomerating agent of-MnS has dual group and turns usefulness into.The as cast condition iron phase presents a shape.Silicon forms a shape and corynebacterium (see figure 2) mutually after the thermal treatment.720 ℃ of insulations are after 2 hours, and iron phase still is, granular, and the granular silicon phase amount obviously increases (see figure 3).After the remelting, fine strip shape iron phase and corynebacterium silicon phase amount increase, and illustrate that compound modifier has slight decay (see figure 4).

Embodiment 3:P becomes ZL108 piston alloy chemical ingredients and is Si12.20%, Mg0.68%, Cu1.38%, Mn0.61%, Fe0.91%.Under industrial condition, melt with resistance furnace.After molten clear, be heated to 700 ℃ with nitrogen or C ₂Cl ₆Degas.Be warming up to 760 ℃ and add Cu-8%P alloy and MoS ₂(add-on 0.3%).Stir, left standstill casting of piston 15 minutes.Adopt water-cooled metal mould, the mould temperature is between 250-300 ℃.Other pours into a mould standard gold genotype coupon, measures alloy mechanical performance and observes metallographic structure.P-MoS ₂Effectively deteriorating time can continue 3-4 hour.Part and coupon all carry out T6 thermal treatment.Fig. 5 enumerates the heat treatment state metallographic structure, has following characteristics: 1. iron phase be, granular, be mingled with a little little plum blossom shape tissue; 2. Eutectic Silicon in Al-Si Cast Alloys is most of disconnects, and is a corynebacterium and a shape.Alloy strength increases, and elongation is significantly improved (seeing Table 3), and is close with external similar alloy.

Table 3 high ferro zl108 alloy mechanical property

	Tensile strength MPa	Elongation %	Hardness HB
				Without MoS 2Handle	??(255-265) ??262	????0	??112
Through MoS 2Handle	??(260-295) ??2270	????1.40	??120

Embodiment 4

Sb becomes the ZL 109 alloy chemical ingredients and is Si11.98%, Mg0.95%, Cu1.00%, Mg0.20%, Ni1.09%, Fe0.85%, Sb0.20%.Fusing, refining, pouring technology such as example one.Temperature of aluminum liquid rises to 720 ℃, can add Al-10%Sb master alloy and MoS ₂(add-on is 0.5%).

Sb-MoS ₂After the combination treatment, no matter as cast condition still to be the heat treatment state alloy microscopic structure all take place noticeable change (see Table 4 and Fig. 6).Have in as-cast structure the tiny needle-like iron phase, most iron phase morphology is group, and is granular, and more primary aluminium dendrite phase occurs.Cast silicone phase morphology and Sr become and organize similarly, after the solution treatment, change into granularly, are corynebacterium (Fig. 7) on a small quantity, Sb-MoS ₂Two-phase group turns into continuing more than 4 hours, does not disappear after the remelting.

Table 4Sb becomes ZL 109 alloy through MoS ₂Microstructure after the processing

State	The silicon phase	Iron phase	The primary aluminium phase	Remarks
					As cast condition	Corynebacterium	Granular, fine acicular	Dendrite quantity is many	Available sylvite or sodium salt are done topped dose
Heat treatment state	Granular, corynebacterium	Granular, bulk
			Be incubated 2 hours as cast condition	Granular, corynebacterium	Granular
Be incubated 2 hours, heat treatment state	Granular	Granular

Embodiment 5

P becomes the hypereutectic Al-Si alloy composition and is Si18.0%, Cu1.1%, Mg0.60%, Mn0.25%, Fe0.68%.With the resistance furnace fusing, use N when being warming up to 700 ℃ ₂Or C ₂Cl ₆Degas, to 800 ℃ of adding Cu-8%P alloys 0.1% and MoS20.6%.850 ℃ are incubated down and the cast sample.300 ℃ of metal pattern die temperature.Alloy is handled through T6.The iron phase of this alloy is a plum blossom shape and a shape, is evenly distributed on the matrix.Eutectic is tiny sheet, but twists more.Primary silicon is tiny, and size is between 20-30 μ m.

Embodiment 6

The ZL401 alloy composition is Zn11.5-12.5%, Si 6.5-7..5%, and Mg0.1-0.3%, Mn 0.25-0.30%, Fe 0.7%.Industrial condition is used the resistance furnace melted alloy down.Fusing, refining, pouring technology such as example one.Add MoS when being warming up to 700 ℃ ₂0.3%.Workpiece is the fire proof motor casing, and requiring has higher water pressure resistance performance, and machined surface must not have pore, cinder hole, pin hole.Workpiece only carries out natural aging.Without MoS ₂The alloy silicon of handling, iron phase is thick needle-like, and primary dendrite aluminium is very thick (see figure 8) mutually.Through MoS ₂Handle the back iron phase and be corynebacterium, part is the hour hand shape, reaches design requirements.Silicon is short strip shape mutually, and part is rotten.Primary aluminium phase secondary dendrite arm spacing obviously reduces (see figure 9).Be incubated three hours and do not find the metamorphism decline.

MoS is used in the explanation of this example separately ₂Effect not as good as MoS ₂-Sb (or P or Sr) combination treatment, and solution treatment is to obtain the mutually indispensable technological process of groupization silicon.

Table 5MoS ₂ZL401 alloy microscopic structure and mechanical property contrast before and after handling

State	Microstructure			Mechanical property
							The silicon phase	Iron phase	The primary aluminium phase	The strong MPa of tension	Unit elongation %	Hardness HB
	Without MoS 2Handle	Thick pin, sheet	Thick needle-like	Large dendritic crystal	??152-182 ??167	??1.0-1.6 ??1.3							????78-80
Through MoS 2Handle							Short strip shape, part is rotten	Corynebacterium+hour hand shape	Secondary dendrite arm spacing reduces	??193-200 ??196	??1.6-2.4 ??2.0	????78

Claims (6)

1, a kind of aluminium silicon alloy series ferrosilicon two-phase agglomerating agent is characterized in that:

(1). described silicon, iron two-phase agglomerating agent are MoS ₂And/or MnS ₂, MnS ₂Add-on be 0.1-0.8%, the add-on of MnS is 0.1-0.8%, the two mixes add-on is 0.1-0.8%.

(2) silicon, iron two-phase agglomerating agent are a kind of and MoS among P or Sr or the Sb ₂And/or MnS ₂The add-on 0.01-0.10% of P or Sr or Sb, MoS ₂Add-on be 0.1-0.8%, the add-on of MnS is 0.1-0.8%, the two mixes add-on is 0.1-0.8%.

2, according to the described aluminum silicon alloy two-phase of claim 1 agglomerating agent, the component that it is characterized in that aluminium silicon alloy series is a Si 6.0-20.0% (weight, down together), Cu 0.5-5.0%, Mg 0.2-1.5%, Ni 0.5-3.0%, Mn 0.1-0.9%, Zn 5.5-13%, Fe＜1.3%, surplus are Al.

3,, it is characterized in that described P, Sr and Sb add with the master alloy form respectively according to the described aluminum silicon alloy two-phase of claim 1 agglomerating agent.

4, aluminium silicon alloy series silicon according to claim 1, iron two-phase agglomerating agent is characterized in that described agglomerating agent or for a kind of in nickelous sulfide, chromic sulfide or the cobaltous sulfide.

5, a kind of aluminium silicon alloy series silicon, iron two-phase groupization treatment process is characterized in that the melting aluminum silicon alloy, are warming up to above 150 ℃ of liquidus line, add agglomerating agent, stir, and leave standstill 15 minutes, and be promptly pourable.Thermal treatment comprises solution treatment and ageing treatment.

6, by group's treatment process of the described alloy series silicon of claim 5, iron two-phase agglomerating agent, it is characterized in that described thermal treatment solid solution treatment process is 510 ℃ ± 5 ℃, heats 4-6 hour.

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