EP0559694B1 - Method of preparing improved hyper-eutectic alloys and composites based thereon - Google Patents
Method of preparing improved hyper-eutectic alloys and composites based thereon Download PDFInfo
- Publication number
- EP0559694B1 EP0559694B1 EP91920402A EP91920402A EP0559694B1 EP 0559694 B1 EP0559694 B1 EP 0559694B1 EP 91920402 A EP91920402 A EP 91920402A EP 91920402 A EP91920402 A EP 91920402A EP 0559694 B1 EP0559694 B1 EP 0559694B1
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- EP
- European Patent Office
- Prior art keywords
- particles
- alloy
- refractory
- eutectic
- hyper
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
Definitions
- This invention relates to a method of preparing improved hyper-eutectic alloys and metal matrix composites containing such alloys.
- Metal matrix composite materials have gained increasing acceptance as structural materials. Such composites typically are composed of reinforcing particles, such as fibres, grit, powder or the like that are embedded within a metallic matrix.
- the reinforcement imparts strength, stiffness and other desirable properties to the composite, while the matrix protects the fibres and transfers load within the composite.
- the two components, matrix and reinforcement thus cooperate to achieve results which are improved over what either could provide on its own.
- a typical composite is an aluminum alloy reinforced with particles of silicon carbide or alumina.
- a major difficulty in the production of good quality metal matrix composites is segregation of the reinforcing particles.
- the segregation of particles occurs in the liquid state as well as during solidification.
- the segregation in the liquid state can be overcome by a proper mixing of the liquid.
- the particles may still segregate during solidification.
- the reinforcing particles can be rejected ahead of the solidification interface, and may agglomerate in the interdendritic liquid which solidifies last.
- reinforcement particles are pushed by the solidification interface or are engulfed is primarily dependent upon the degree of wetting between the particles and the solid surface. If the solid surface wets the particles, they are engulfed by the solid surface. In this case the particle distribution in the solidified material is as uniform as it was in the liquid state. On the other hand, if the solid surface, e.g. aluminum dendrite surface, does not wet the particles, they are pushed away, resulting in interdendritic segregation.
- intermetallic compounds may precipitate directly from a melt of the alloy. These intermetallic compounds often tend to be coarse, brittle particles, and these particles tend to segregate due to density difference, particularly when the solidification rate is slow.
- a hypereutectic LM30 Al-Si alloy containing 3 wt.% of graphite particles is analyzed.
- the LM30 alloy specification defines an alloy composition which contains,among others, from 16 to 18 wt.% Si, from 0.3 to 0.7 wt.% Mg, up to 1.1 wt.% Fe, and up to 0.3 wt.% Mn.
- Fig. 2 shows a preferential nucleation of primary silicon on the surface of the graphite.
- non-metallic refractory particles when added to a molten hyper-eutectic Al-Si-Mn alloy can be engulfed durina solidification by an intermetallic phase which solidifies first from the molten hypereutectic alloy during solidification thereof such that the refractory particles are engulfed by the intermetallic phase as it grows during solidification. Because the intermetallics engulf the refractory particles, there is no longer a tendency for the refractory particles to segregate to the interdendritic regions and they remain homogeneously distributed throughout an as-solidified ingot. The presence of excess alloying elements in the hyper-eutectic alloy beyond eutectic amounts is the mechanism for the formation of the desired intermetallic phase and this intermetallic phase forms automatically during cooling provided the alloy being cooled is a hyper-eutectic alloy.
- One embodiment of the invention is a method for preparing a composite of an aluminum alloy and particles of a non-metallic refractory material, which comprise melting an aluminum alloy; adding particles of non-metallic refractory material to the molten aluminum matrix; mixing together the molten aluminum alloy and the particles of refractory material; and casting the resulting mixture.
- the aluminum alloy is a hyper-eutectic aluminum alloy comprising, in percentages by weight, 7-16% silicon, 0.5-3.0% manganese, 0-5.0% copper, 0-5.0% nickel, 0-1.0% iron, 0-0.2% titanium and 0.3-2.0% magnesium and the balance of the alloy being aluminum and inevitable impurities and the excess alloying element or elements of the hyper-eutectic molten aluminum alloy solidify first from the molten aluminum matrix during solidification thereof to form intermetallics comprising Mn 3 Si 2 Al 15 which engulf said refractory particles and keep them homogeneously distributed throughout the solidified product.
- the refractory particles act as a refiner for precipitating intermetallics.
- the use of unreinforced hyper-eutectic alloys is very restricted because they often form coarse, brittle intermetallic particles on solidification, and the intermetallic particles tend to segregate due to the density difference, particularly when the solidification rate is not rapid.
- phosphorus additions and fluxing have previously been required to refine the primary silicon to a size suitable for good wear properties.
- the efficiency of phosphorus to refine primary silicon decreases with increasing holding time of the melt, complicating the casting practice.
- refractory particles such as silicon carbide particles
- the addition of refractory particles, such as silicon carbide particles, according to the present invention can nucleate and refine these intermetallics, as well as modify their morphology, so that the deleterious effect of coarse intermetallics is reduced. This is of particular value for alloys that are intended for high temperature use.
- Such high temperature alloys may be used in casting applications, or as wrought products, such as forgings and extrusions.
- the alloy composites of this invention in which the refractory particles act as a refiner for precipitating intermetallics have superior high temperature strength, making them useful for applications such as cast brake rotors.
- the refractory particles may also serve as reinforcing particles in a composite with a hyper-eutectic alloy.
- they may be used not only to refine a hyper-eutectic alloy, but also to form a composite therewith.
- the particles are typically used in very small sizes, e.g. less than 1 ⁇ m.
- they when they are used also for reinforcing the alloy, they may be used in much larger sizes, e.g. up to 20 ⁇ m.
- For reinforcing they are typically used in sizes in the range of 5-20 ⁇ m and preferably 10-15 ⁇ m.
- the non-metallic refractory material is preferably a metal oxide, metal nitride, metal carbide or metal silicide.
- the most preferred refractory material is silicon carbide or aluminum oxide particulate.
- the procedure of the present invention for making a composite functions best with reinforcing particles which are relatively equi-dimensional, e.g. having an aspect ratio in any direction of no more than 5:1.
- the reinforcing particles are typically added in amounts of 5-40% by volume, preferably 10-25% by volume. It has been found that silicon carbide reinforcing particles are engulfed by silicon crystals formed during solidification of the composite.
- the invention also relates to new aluminum alloy products having improved high temperature properties.
- One of the novel products is a particle reinforced aluminum alloy casting in which the alloy is a hyper-eutectic alloy and the excess alloying element or elements of the hypereutectic alloy have solidified first from the molten metal matrix and have formed intermetallics during solidification which have engulfed the refractory particles and kept them homogeneously distributed throughout the solidified product.
- Another novel product is a refined aluminum alloy casting in which intermetallics formed during solidification are uniformly dispersed as fine particles because of the refining effect of particles of non-metallic refractory material contained in the alloy.
- the alloy of the novel products is a hyper-eutectic aluminum alloy containing silicon, magnesium and manganese, preferably in the amounts 7-16 wt% silicon, 0.5-3.0 wt% manganese, 0-5.0 wt% copper, 0-5.0 wt% nickel, 0-1.0 wt% iron, 0-0.2 wt% titanium and 0.3-2.0 wt% magnesium and the balance of the alloy being aluminum and inevitable impurities.
- the silicon assists fluidity and stabilizes the refractory particles; below 7% silicon the refractory material tends to be unstable while above 16% coarse intermetallics are formed and the composite becomes embrittled.
- the magnesium improves wetting and provides strengthening; below 0.3% magnesium the wetting is poor, while above 2% there is shrinkage porosity.
- the manganese forms intermetallics providing uniform refractory particle distribution and improved high temperature strength; below 0.5% manganese there is no improvement in high temperature strength and above 3.0% the casting temperature becomes too high.
- the alloy also preferably contains up to 5.0 wt% copper. This improves elevated temperature strength with amounts above 5.0% providing poor casting fluidity and embrittlement.
- Another optional component is nickel which may also be present in amounts up to 5.0 wt%. It also improves elevated temperature strength, although amounts above 5.0% cause coarse intermetallics and embrittlement.
- a further common optional element is iron which may be present in amounts up to 1.0 wt%. At amounts above 1.0 wt% there is the danger of forming coarse intermetallics which cannot be refined by the refractory particles.
- the alloy may also contain up to 0.2 wt%, preferably 0.1-0.2 wt%, titanium as a grain refiner.
- Alloys of particular interest for high temperature applications are those containing substantial amounts of Mn.
- Such alloys may be produced by adding Mn to traditional high temperature alloy compositions until the hyper-eutectic range is reached. This is mixed with refractory particles, e.g. which refine the intermetallics and distribute the particles uniformly throughout the matrix.
- intermetallic While a typical intermetallic is a compound formed of at least two metallic components, within the process of this invention, silicon behaves in the manner of an intermetallic in its ability to wet and engulf refractory particles. Accordingly, the term "intermetallic" as used in this invention includes silicon.
- An aluminum matrix composite was prepared by mixing 15% by volume of silicon carbide particles having sizes in the range of 10-15 ⁇ m with a melt of A356 aluminum alloy containing 6.5 to 7.5% Si and 0.3 to 0.45% Mg. This was cast and solidified to form an ingot having the microstructure shown in Figure 1. It will be seen that the reinforcing particles have been pushed ahead of the solidification interface and are not uniformly dispersed throughout the ingot.
- Another ingot was prepared from a melt of Al - 16% Si alloy and 15% by volume of silicon carbide particles having particle sizes in the range of 10-15 ⁇ m. These were thoroughly mixed and the mixture was then cast and solidified to form an ingot.
- the ingot formed had the microstructure shown in Figure 2 and it will be seen that the reinforcing particles are uniformly spaced and are engulfed by silicon crystals.
- the silicon carbide particles also refined the silicon.
- Two melts were prepared by heating aluminum containing 16 wt% silicon to a temperature of 750°C.
- One melt was cast "as is” to form an ingot and a second melt was mixed with 15% by volume of silicon carbide particles having sizes in the range of 10-15 microns and then cast to form an ingot.
- the ingots were identical in size and were cooled and solidified under identical conditions.
- Figure 8 shows the microstructure of the ingot without the refractory particles
- Figure 9 shows the microstructure of the ingot with the refractory particles. The refinement of the silicon is clearly evident.
- Example 2 To illustrate the effectiveness of the refinement according to this invention, the procedure of Example 2 was repeated using a melt of Al - 7% Si - 2% Mn alloy. One cast ingot was made from the alloy itself and a second cast ingot was made from a composite of the alloy and 15% by volume of silicon carbide particles. Fig. 10 shows the microstructure of the cast alloy and Fig. 11 shows the microstructure of the cast composite. It can be seen that the primary Mn 3 Si 2 Al 15 intermetallic dendrites in the cast alloy are completely refined by the SiC particles.
- Three aluminum matrix composites were prepared by mixing 15% by volume of silicon carbide particles having sizes in the range of 10-15 ⁇ m with three different aluminum alloy melts.
- the matrix alloys had the following compositions:
- the composites so formed were cast and solidified in the form of 12.7 mm diameter as-cast test bars and 57 mm diameter ingots.
- the as-cast test bars were held for 100 hours at 250°C, and tensile tested at the soak temperature.
- the 57 mm diameter ingots were extruded at 450°C to 9.5 mm diameter rod.
- Test bars were machined from the rod, and held at between 200 and 400°C for various times to examine the effect of long time exposure on the high temperature strength. The results are shown in Figure 12-15.
- High temperature composite alloys may be used in casting applications, or as wrought products such as forgings and extrusions.
- Figure 12 shows the strength retention of as-cast material after 100 hrs at 250°C, which is relevant for applications such as cast brake rotors. The figure shows that the new alloy composites have superior high temperature strength to the presently used A356-SiC composite. It is also apparent that adding SiC reinforcement to the unreinforced alloys adds to the high temperature performance of these materials.
- the invention provides techniques for improving hyper-eutectic alloys, which alloys can be used for the manufacture of a variety of industrial products by conventional techniques.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
Description
Alloy | Intermetallic |
Al - 16 wt% Si --- | Si |
Al - 12 wt% Si - 1.5 wt% Fe | FeSiAl5 |
Al - 7 wt% Si - 2 wt% Fe | Fe2SiAl8 |
Al - 12 wt% Si - 1.5 wt% Mn | Mn3Si2Al15 |
Al - 11 wt% Si - 5 wt% Ni | NiAl3 |
Al - 10 wt% Si - 10 wt% Mg | Mg2Si |
Al - 10 wt% Si - 2 wt% Cr | Cr5Si8Al2 |
Al - 16 wt% Si - 0.3 wt% Ti | Ti(AlSi)2 |
Al - 10 wt% Si - 0.5 wt% Zr | ZrAl3 |
Alloy |
Al-10 wt% Si-1.2 wt% Mn-0.4 wt% Mg-15 vol% SiC |
Al-10 wt% Si-1.2 wt% Mn-0.4 wt% Mg-5 wt% Ni-15 vol% SiC |
Al-10 wt% Si-1.2 wt% Mn-1.0 wt% Mg-5 wt% Ni-2.5 wt% Cu -15 vol% SiC |
- Alloy A:
- Al - 10 wt% Si - 1.2 wt% Mn - 0.4 wt% Mg
- Alloy B:
- Al - 10 wt% Si - 1.2 wt% Mn - 0.4 wt% Mg - 5 wt% Ni
- Alloy C:
- Al - 10 wt% Si - 1.2 wt% Mn - 1.0 wt% Mg - 5 wt% Ni - 2.5 wt% Cu
Claims (16)
- A method for preparing a composite of an aluminum alloy and particles of a non-metallic refractory material, comprising:melting an aluminum alloy;adding particles of non-metallic refractory material to the molten aluminum matrix;mixing together the molten aluminum alloy and the particles of refractory material; andcasting the resulting mixture;
- A method according to claim 1 characterized in that the refractory particles are selected from the group consisting of a metal oxide, metal nitride, metal carbide and metal silicide.
- A method according to claim 2 characterized in that the refractory particles comprise silicon carbide.
- A method according to any one of claims 1-3 characterized in that the refractory particles are reinforcing particles and have sizes up to 20 µm.
- A method according to any one of claims 1-3 characterized in that the refractory particles are reinforcing particles having sizes in the range of 10 - 15 µm.
- A method according to any one of claims 1-3 characterized in that the refractory particles have sizes of less than 1 µm.
- A method according to claim 6 characterized in that the refractory particles nucleate and refine the intermetallics.
- An aluminum alloy composite casting comprising a matrix of aluminum alloy having dispersed therethrough particles of non-metallic refractory material,
characterized in that the aluminum alloy is an Al-Si-Mn hyper-eutectic alloy comprising, in percentage by weight, 7-16% silicon, 0.5-3.0% manganese, 0-5.0% copper, 0-5.0% nickel, 0-1.0% iron, 0-0.2% titanium and 0.3-2.0% magnesium and the balance of the alloy being aluminum and inevitable impurities, in which the excess alloying element or elements of the hyper-eutectic alloy have solidified first from the molten aluminum matrix and have formed intermetallics comprising Mn3Si2Al15 during solidification which have engulfed the refractory particles and kept them homogenerously distributed throughout the solidified product. - A casting according to claim 8 characterized in that the refractory particles are selected from the group consisting of a metal oxide, metal nitride, metal carbide and metal silicide.
- A casting according to claim 8 characterized in that the refractory particles comprise silicon carbide.
- A casting according to any one of claims 8-10 characterized in that the refractory particles have sizes up to 20 µm.
- A casting according to any one of claims 8-10 characterized in that the refractory particles have sizes in the range of 10 - 15 µm.
- A casting according to any one of claims 8-10 characterized in that the refractory particles have sizes of less than 1 µm.
- A casting according to any one of claims 8-13 characterized in that the particles have an aspect ratio in any direction of no more than 5:1.
- A casting according to any one of claims 8-14 characterized in that the particles are present in an amount of 5-40% by volume.
- A casting according to any one of claims 8-15 characterized in that titanium is present in the alloy in an amount of 0.1-0.2%.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002030928A CA2030928A1 (en) | 1990-11-27 | 1990-11-27 | Method of preparing improved eutectic or hyper-eutectic alloys and composites based thereon |
CA2030928 | 1990-11-27 | ||
US77012491A | 1991-10-02 | 1991-10-02 | |
US770124 | 1991-10-02 | ||
PCT/CA1991/000418 WO1992009711A1 (en) | 1990-11-27 | 1991-11-27 | Method of preparing eutectic or hyper-eutectic alloys and composites based thereon |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0559694A1 EP0559694A1 (en) | 1993-09-15 |
EP0559694B1 true EP0559694B1 (en) | 1998-09-16 |
Family
ID=25674383
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91920402A Expired - Lifetime EP0559694B1 (en) | 1990-11-27 | 1991-11-27 | Method of preparing improved hyper-eutectic alloys and composites based thereon |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0559694B1 (en) |
JP (1) | JP3492681B2 (en) |
DE (1) | DE69130227T2 (en) |
WO (1) | WO1992009711A1 (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6086688A (en) * | 1997-07-28 | 2000-07-11 | Alcan International Ltd. | Cast metal-matrix composite material and its use |
GB9804599D0 (en) * | 1998-03-05 | 1998-04-29 | Aeromet International Plc | Cast aluminium-copper alloy |
JP3690171B2 (en) | 1999-03-16 | 2005-08-31 | 株式会社日立製作所 | Composite material and its production method and application |
US8540797B2 (en) | 2008-07-29 | 2013-09-24 | Indian Institute Of Science | Process for preparation of nano ceramic-metal matrix composites and apparatus thereof |
CN101787454B (en) * | 2010-04-12 | 2011-11-23 | 中国船舶重工集团公司第十二研究所 | Method for preparing multicomponent reinforced aluminum-base composite material |
US10370742B2 (en) | 2013-03-14 | 2019-08-06 | Brunswick Corporation | Hypereutectic aluminum-silicon cast alloys having unique microstructure |
US9650699B1 (en) | 2013-03-14 | 2017-05-16 | Brunswick Corporation | Nickel containing hypereutectic aluminum-silicon sand cast alloys |
US9109271B2 (en) * | 2013-03-14 | 2015-08-18 | Brunswick Corporation | Nickel containing hypereutectic aluminum-silicon sand cast alloy |
KR101964347B1 (en) * | 2017-11-06 | 2019-04-01 | 한국생산기술연구원 | Aluminium alloy die-casting products and manufacturing method thereof |
CN114210987B (en) * | 2021-12-21 | 2022-12-09 | 上海交通大学 | High-volume-fraction particle reinforced titanium-based composite material powder and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3993478A (en) * | 1972-02-09 | 1976-11-23 | Copper Range Company | Process for dispersoid strengthening of copper by fusion metallurgy |
US3951651A (en) * | 1972-08-07 | 1976-04-20 | Massachusetts Institute Of Technology | Metal composition and methods for preparing liquid-solid alloy metal compositions and for casting the metal compositions |
JPS58110652A (en) * | 1981-12-25 | 1983-07-01 | Nissan Motor Co Ltd | Wear resistant composite aluminum material and its manufacture |
-
1991
- 1991-11-27 JP JP50021892A patent/JP3492681B2/en not_active Expired - Fee Related
- 1991-11-27 DE DE69130227T patent/DE69130227T2/en not_active Expired - Fee Related
- 1991-11-27 EP EP91920402A patent/EP0559694B1/en not_active Expired - Lifetime
- 1991-11-27 WO PCT/CA1991/000418 patent/WO1992009711A1/en active IP Right Grant
Non-Patent Citations (4)
Title |
---|
Aluminum Alloys: Structure and Properties, L.F. Mondolfo, Butterworths, 1976, pp.592-594 * |
Fabrication of particulates reinforced metal composites, Materials Park, OH, ASM International, Ed.J.Masounave et al., 1990, pp.47-52 * |
Int. Mtrls Rev., 1986, 31(3), pp.115-139 * |
Z. Metallkde, 1989, 80(M-6), pp.444-446 * |
Also Published As
Publication number | Publication date |
---|---|
EP0559694A1 (en) | 1993-09-15 |
DE69130227T2 (en) | 1999-01-21 |
JPH06502689A (en) | 1994-03-24 |
WO1992009711A1 (en) | 1992-06-11 |
JP3492681B2 (en) | 2004-02-03 |
DE69130227D1 (en) | 1998-10-22 |
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