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EP0668806B1 - Silicon alloy, method for producing the alloy and method for production of consolidated products from silicon alloy - Google Patents

Silicon alloy, method for producing the alloy and method for production of consolidated products from silicon alloy Download PDF

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Publication number
EP0668806B1
EP0668806B1 EP94901077A EP94901077A EP0668806B1 EP 0668806 B1 EP0668806 B1 EP 0668806B1 EP 94901077 A EP94901077 A EP 94901077A EP 94901077 A EP94901077 A EP 94901077A EP 0668806 B1 EP0668806 B1 EP 0668806B1
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EP
European Patent Office
Prior art keywords
weight
silicon
based alloy
alloy
elements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94901077A
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German (de)
French (fr)
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EP0668806A1 (en
Inventor
Leif L'estrade
Karl Forwald
Gunnar Schüssler
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Elkem ASA
Original Assignee
Elkem ASA
Elkem Materials AS
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys

Definitions

  • the present invention relates to silicon based aluminium and titanium-containing alloys and powder-based products produced from such alloy.
  • the invention further relates to a method for producing silicon based aluminium- and titanium-containing alloys and a method for producing shaped articles from such alloys.
  • Silicon has up till now been used as a raw material for producing silanes, electronic products and as an alloying element for steel and aluminium.
  • silicon is normally added in the form of ferrosilicon in amounts normally below 4 % by weight of silicon.
  • silicon is added as elemental silicon.
  • the content of silicon in aluminium alloys varies, but may, for aluminium-silicon alloys, be added in an amount of maximum 20 % by weight of the alloys.
  • Elemental silicon is very brittle and lacks ductility. Addition of silicon to for example aluminium alloys thus causes an increased brittleness of the alloys when the silicon content exceeds about 20 % by weight. As far as the inventors know, there does not exist silicon-based alloys which have such properties that the alloy can be used for structural purposes.
  • Silicon has, however, a number of properties which makes use of silicon-based alloys very interesting for structural applications.
  • silicon has a low density of 2.3 g/cm 3 and a high melting point of 1410°C.
  • Silicon based alloys having a sufficient ductility and strength would thus have a number of advantages compared with other light metals such as for example Al, Ti, Mg and Be. This relates particularly to properties like high stiffness in relation to weight, low thermal expansion, high resistance to corrosion, high resistance against erosion, and use at higher temperatures than other light metals.
  • the present invention relates to a rapidly solidified silicon-based alloy, which alloy contains 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr, P, the rest, except for normal impurities, being silicon in an amount of at least 35 % by weight.
  • the silicon alloy contains 10 - 30 % by weight Al and 3 - 15 % by weight Ti.
  • the silicon alloy contains 2 - 10 % by weight Al and 25 - 40 % by weight Ti.
  • the alloy according to the present invention contains preferably boron in an amount of 0.01 - 0,1 % by weight, and/or phosphorous in an amount of 0.01 - 0.05 % by weight and/or strontium in an amount of 0.05 - 0.5 % by weight.
  • the content of the elements V, Cr, Mn, Fe, Ni and Co is preferably between 1 and 3 % by weight.
  • the rapidly solidified alloy has preferably a primary grain size of less than 50 micron and more preferred less than 10 micron. In order to obtain a highest possible strength and ductility it is particularly preferred that the solidified alloy and precipitated intermetallic phases have a primary grain size of less than 1 micron.
  • the present invention relates to a method for production of rapidly solidified silicon-based alloy, said method being characterized in that it is provided a molten alloy containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni and Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities, being silicon in an amount of at least 35 % by weight, which melt is solidified at a rate of at least 10 3 °C/second.
  • the melt is solidified at a rate of between 10 4 and 10 6 °C/second.
  • the solidification is preferably done by melt spinning or by gas atomization. It is, however, within the scope of the present invention to use other known methods to achieve a sufficiently high solidification rate.
  • the present invention relates to a method for producing consolidated articles from rapidly solidified silicon-based alloy wherein rapidly solidified silicon-based alloy containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities, being silicon in an amount of at least 35 % by weight, is crushed and milled to a particle size below 500 microns and formed to articles by means of powdermetallurgical methods, whereafter the formed articles is hot consolidated.
  • the rapidly solidified silicon-based alloy is milled to a particle size below 200 microns before the articles are formed.
  • Forming of articles and consolidation of the formed articles are done by conventional powdermetallurgical methods. It is preferred to use hot isostatic pressing, but it is within the scope of the present invention to use for example cold isostatic pressing followed by sintering, hot single axial pressing, forging, extruding and injectioncasting followed by sintering.
  • the consolidated articles made from the silicon-based alloy according to the present invention have very high compression strength and a sufficiently high ductility in order that the products can be used for structural purposes.
  • the rods were used as a raw material for melt spinning. By the melt spinning the rods were melted and cast to thin sheets or ribbons with a solidification rate of above 10 4 °C/second.
  • the ribbons were milled in a closed mill to a particle size of less than 200 microns.
  • the alloy particles were thereafter filled into a cylinder-shaped mould having a diameter of 1 cm and a height of more than 1 cm.
  • the alloy particles were thereafter pressed for two hours using single-axial pressure of 40 MPa and at a temperature of 700°C.
  • the produced articles were thereafter tested by compression.
  • the ultimate strength was measured to 878 MPa and the change in length during compression was 7 %.
  • Alloys 1 through 5 were subjected to hot pressing and the fracture strength and compression length were measured. The results are shown in Table I. Hot pressing parameters Fracture Strength (MPa) Compression Length % Alloy Temp (°C) Time (min.) Load (kg) 1 700 120 530 1196 7.5 2 700 120 420 926 5.4 3 625 120 420 723 5.4 4 700 120 420 978 7.7 5 1125 120 420 664 5.9
  • Table 2 shows that the hot pressed products obtained a very high strength and a good compression length.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates to a rapidly solidified silicon-based alloy, containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0-10 % by weight of one or more of the elements V, Cr, Fe, Mn, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities being silicon in an amount of at least 35 % by weight. The invention further relates to a method for producing such alloys where a molten alloy is provided and is solidified at a rate of solidification of at least 10<3> DEG C/second. Consolidated products are produced from the silicon based alloy by forming articles from powdered alloy and consolidating the formed articles.

Description

Technical Field
The present invention relates to silicon based aluminium and titanium-containing alloys and powder-based products produced from such alloy. The invention further relates to a method for producing silicon based aluminium- and titanium-containing alloys and a method for producing shaped articles from such alloys.
Background Art
Silicon has up till now been used as a raw material for producing silanes, electronic products and as an alloying element for steel and aluminium. When used as an alloying element for steel, silicon is normally added in the form of ferrosilicon in amounts normally below 4 % by weight of silicon. When used as an alloying element for aluminium and aluminium alloys silicon is added as elemental silicon. The content of silicon in aluminium alloys varies, but may, for aluminium-silicon alloys, be added in an amount of maximum 20 % by weight of the alloys.
Elemental silicon is very brittle and lacks ductility. Addition of silicon to for example aluminium alloys thus causes an increased brittleness of the alloys when the silicon content exceeds about 20 % by weight. As far as the inventors know, there does not exist silicon-based alloys which have such properties that the alloy can be used for structural purposes.
Silicon has, however, a number of properties which makes use of silicon-based alloys very interesting for structural applications. Thus silicon has a low density of 2.3 g/cm3 and a high melting point of 1410°C. Silicon based alloys having a sufficient ductility and strength would thus have a number of advantages compared with other light metals such as for example Al, Ti, Mg and Be. This relates particularly to properties like high stiffness in relation to weight, low thermal expansion, high resistance to corrosion, high resistance against erosion, and use at higher temperatures than other light metals.
In the following table there is shown some properties for silicon compared to the same properties for Mg, Al, Ti, and stainless 18/8 steel.
Si Mg Al Ti 18/8 steel
Density (g/cm3) 2.3 1.7 2.7 4.5 8.1
E-module (GPa) 113 44 71 106 200
Stiffness/density-ratio 4.8 2.1 2.6 2.4 2.5
Melting point (°C) 1410 650 660 1660 1400
Thermal expansion (10-6/K) 2.5 26 23 10 18
Thermal conductivity (J/smK) 84 160 190 19 14
Heat capacity (J/gK) 0.71 1.03 0.90 0.53 0.48
Disclosure of Invention
It is an object of the present invention to provide silicon-based alloys having such a ductility and strength that the alloys can be used for structural purposes and where the alloys still have the good properties of silicon.
Thus, according to a first aspect the present invention relates to a rapidly solidified silicon-based alloy, which alloy contains 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr, P, the rest, except for normal impurities, being silicon in an amount of at least 35 % by weight.
According to a preferred embodiment, the silicon alloy contains 10 - 30 % by weight Al and 3 - 15 % by weight Ti.
According to another preferred embodiment the silicon alloy contains 2 - 10 % by weight Al and 25 - 40 % by weight Ti.
The alloy according to the present invention contains preferably boron in an amount of 0.01 - 0,1 % by weight, and/or phosphorous in an amount of 0.01 - 0.05 % by weight and/or strontium in an amount of 0.05 - 0.5 % by weight. The content of the elements V, Cr, Mn, Fe, Ni and Co is preferably between 1 and 3 % by weight.
The rapidly solidified alloy has preferably a primary grain size of less than 50 micron and more preferred less than 10 micron. In order to obtain a highest possible strength and ductility it is particularly preferred that the solidified alloy and precipitated intermetallic phases have a primary grain size of less than 1 micron.
According to a second aspect, the present invention relates to a method for production of rapidly solidified silicon-based alloy, said method being characterized in that it is provided a molten alloy containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni and Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities, being silicon in an amount of at least 35 % by weight, which melt is solidified at a rate of at least 103 °C/second.
According to a preferred embodiment the melt is solidified at a rate of between 104 and 106 °C/second.
The solidification is preferably done by melt spinning or by gas atomization. It is, however, within the scope of the present invention to use other known methods to achieve a sufficiently high solidification rate.
According to a third aspect the present invention relates to a method for producing consolidated articles from rapidly solidified silicon-based alloy wherein rapidly solidified silicon-based alloy containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities, being silicon in an amount of at least 35 % by weight, is crushed and milled to a particle size below 500 microns and formed to articles by means of powdermetallurgical methods, whereafter the formed articles is hot consolidated.
According to a preferred embodiment the rapidly solidified silicon-based alloy is milled to a particle size below 200 microns before the articles are formed.
Forming of articles and consolidation of the formed articles are done by conventional powdermetallurgical methods. It is preferred to use hot isostatic pressing, but it is within the scope of the present invention to use for example cold isostatic pressing followed by sintering, hot single axial pressing, forging, extruding and injectioncasting followed by sintering.
It has surprisingly been found that the consolidated articles made from the silicon-based alloy according to the present invention have very high compression strength and a sufficiently high ductility in order that the products can be used for structural purposes.
By rapid solidification of the silicon-based alloy according to the present invention it is obtained a very fine grained material which has an exceptional good distribution of intermetallic phases in the material and very small grains. It is assumed that it is this combination which give the material its high ductility and high strength. By hot consolidation of the articles according to the present invention, it is important to use such a combination of temperature and pressure that the finished products become sufficiently dense and that grain growth during the consolidation process is not effecting the properties of the material.
Detailed description of preferred embodiments. EXAMPLE 1
A silicon alloy containing 25 % by weight of Al, 5 % by weight of Ti, the rest except for normal impurities, being silicon, was melted in a vacuum furnace and cast in the form of rods. The rods were used as a raw material for melt spinning. By the melt spinning the rods were melted and cast to thin sheets or ribbons with a solidification rate of above 104 °C/second. The ribbons were milled in a closed mill to a particle size of less than 200 microns.
The alloy particles were thereafter filled into a cylinder-shaped mould having a diameter of 1 cm and a height of more than 1 cm. The alloy particles were thereafter pressed for two hours using single-axial pressure of 40 MPa and at a temperature of 700°C.
The produced articles were thereafter tested by compression. The ultimate strength was mesured to 878 MPa and the change in length during compression was 7 %.
The results show that the produced alloy has a very high compression strength and a compression length comparable to fiber-reinforced aluminium.
EXAMPLE 2
Five alloys were made in powder form using the same procedure as described in Example 1.
Alloy 1:
25 % by weight Al, 5 % by weight Ti, 0.01 % Sr, the rest being silicon.
Alloy 2:
15 % by weight Al, 5 % by weight Ti, the rest being silicon.
Alloy 3:
35 % by weight Al, 5 % by weight Ti, the rest being silicon.
Alloy 4:
25 % by weight Al, 5 % by weight Ti, the rest being silicon.
Alloy 5:
5 % by weight Al, 35 % by weight Ti, the rest being silicon.
Alloys 1 through 5 were subjected to hot pressing and the fracture strength and compression length were measured. The results are shown in Table I.
Hot pressing parameters Fracture Strength (MPa) Compression Length %
Alloy Temp (°C) Time (min.) Load (kg)
1 700 120 530 1196 7.5
2 700 120 420 926 5.4
3 625 120 420 723 5.4
4 700 120 420 978 7.7
5 1125 120 420 664 5.9
Table 2 shows that the hot pressed products obtained a very high strength and a good compression length.

Claims (12)

  1. Rapidly solidified silicon-based alloy consisting of 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities, being silicon in an amount of at least 35 % by weight.
  2. Silicon-based alloy according to claim 1, characterized in that it contains 10 - 30 % by weight Al and 3 - 15 % by weight Ti.
  3. Silicon-based alloy according to claim 1, characterized in that it contains 2 - 10 % by weight Al and 25 - 40 % by weight Ti.
  4. Silicon-based alloy according to claims 1 - 3, characterized in that it contains boron in an amount of 0,01 - 0,1 % by weight.
  5. Silicon-based alloy according to claims 1 - 3, characterized in that it contains phosphorous in an amount of 0.01 - 0.05 % by weight.
  6. Silicon-based alloy according to claims 1 - 3, characterized in that it contains strontium in an amount of 0.05 - 0.5 % by weight.
  7. Silicon-based alloy according to claims 1 - 6, characterized in that it contains at least one of the elements V, Cr, Mn, Fe, Ni and Co in an amount of 1 - 3 % by weight.
  8. Silicon-based alloy according to claims 1 - 7, characterized in that it has a primary grain size of less than 50 micron, preferably less than 10 micron.
  9. Method for production of a rapidly solidified silicon-based alloy, characterized in that it is provided a melt containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities being silicon in an amount of at least 35 % by weight, which melt is solidified at a solidification rate of at least 103 °C/second.
  10. Method according to claim 9, characterized in that the melt is solidified at a solidification rate between 104 and 106 °C/second.
  11. Method for production of consolidated products from rapidly solidified silicon-based alloys, characterized in that it is provided a rapidly solidified silicon-based alloy containing 2 - 40 % by weight Al, 2 - 45 % by weight Ti, 0 - 10 % by weight of one or more of the elements V, Cr, Mn, Fe, Ni, Co, 0 - 1 % by weight of one or more of the elements B, Sr and P, the rest, except for impurities being silicon in an amount of at least 35 % by weight, crushing and milling the rapidly solidified alloy to a particle size below 500 micron, forming articles of the milled particles by powder-metallurgical methods and consolidating the formed articles.
  12. Method according to claim 11, characterized in that the rapidly solidified silicon-based alloy is milled to a particle size below 200 microns before the articles are formed.
EP94901077A 1992-11-18 1993-11-17 Silicon alloy, method for producing the alloy and method for production of consolidated products from silicon alloy Expired - Lifetime EP0668806B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NO924442A NO175543C (en) 1992-11-18 1992-11-18 Silicon-based alloy, process for making such alloy, and process for producing consolidated products from silicon-based alloy
NO924442 1992-11-18
PCT/NO1993/000171 WO1994011138A1 (en) 1992-11-18 1993-11-17 Silicon alloy, method for producing the alloy and method for production of consolidated products from silicon alloy

Publications (2)

Publication Number Publication Date
EP0668806A1 EP0668806A1 (en) 1995-08-30
EP0668806B1 true EP0668806B1 (en) 1998-08-26

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EP94901077A Expired - Lifetime EP0668806B1 (en) 1992-11-18 1993-11-17 Silicon alloy, method for producing the alloy and method for production of consolidated products from silicon alloy

Country Status (7)

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EP (1) EP0668806B1 (en)
JP (1) JP2821269B2 (en)
AT (1) ATE170114T1 (en)
AU (1) AU5578594A (en)
DE (1) DE69320649T2 (en)
NO (1) NO175543C (en)
WO (1) WO1994011138A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
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US10180292B2 (en) 2013-09-26 2019-01-15 Alfa Laval Corporate Ab Plate heat exchanger
US10576587B2 (en) 2013-09-26 2020-03-03 Alfa Laval Corporate Ab Brazing concept

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9514777D0 (en) * 1995-07-19 1995-09-20 Osprey Metals Ltd Silicon alloys for electronic packaging
CN1131570C (en) * 1998-09-08 2003-12-17 住友金属工业株式会社 Negative electrode material for non-aqueous electrolyte secondary battery and manufacturing method thereof
EP1033767B9 (en) * 1998-09-18 2010-09-01 Canon Kabushiki Kaisha Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary cell
US7498100B2 (en) * 2003-08-08 2009-03-03 3M Innovative Properties Company Multi-phase, silicon-containing electrode for a lithium-ion battery
US7767349B2 (en) 2005-07-25 2010-08-03 3M Innovative Properties Company Alloy compositions for lithium ion batteries
US7851085B2 (en) 2005-07-25 2010-12-14 3M Innovative Properties Company Alloy compositions for lithium ion batteries
US7871727B2 (en) 2005-07-25 2011-01-18 3M Innovative Properties Company Alloy composition for lithium ion batteries
US7906238B2 (en) 2005-12-23 2011-03-15 3M Innovative Properties Company Silicon-containing alloys useful as electrodes for lithium-ion batteries
JP5487388B2 (en) * 2009-10-02 2014-05-07 国立大学法人東北大学 Method for producing polycrystalline fibrous silicon and polycrystalline fibrous silicon

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Publication number Priority date Publication date Assignee Title
GB404463A (en) * 1932-06-02 1934-01-18 Aluminium Ltd Improvements in or relating to aluminium silicon alloys and methods of manufacturingthe same
JPS5914096B2 (en) * 1979-09-05 1984-04-03 財団法人電気磁気材料研究所 Al-Si based vibration absorbing alloy and its manufacturing method
US4402905A (en) * 1982-03-05 1983-09-06 Westinghouse Electric Corp. Production of a polycrystalline silicon aluminum alloy by a hot pressing technique
DE3573137D1 (en) * 1984-10-03 1989-10-26 Sumitomo Electric Industries Material for a semiconductor device and process for its manufacture
JPH01205055A (en) * 1988-02-12 1989-08-17 Sumitomo Electric Ind Ltd Substrate material for semiconductor device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10180292B2 (en) 2013-09-26 2019-01-15 Alfa Laval Corporate Ab Plate heat exchanger
US10323890B2 (en) 2013-09-26 2019-06-18 Alfa Laval Corporate Ab Method for joining metal parts
EP2853333B1 (en) * 2013-09-26 2019-08-21 Alfa Laval Corporate AB Method of joining metal parts using a melting depressant layer
US10576587B2 (en) 2013-09-26 2020-03-03 Alfa Laval Corporate Ab Brazing concept

Also Published As

Publication number Publication date
DE69320649D1 (en) 1998-10-01
NO175543C (en) 1994-10-26
DE69320649T2 (en) 1999-04-01
JP2821269B2 (en) 1998-11-05
AU5578594A (en) 1994-06-08
WO1994011138A1 (en) 1994-05-26
NO924442D0 (en) 1992-11-18
ATE170114T1 (en) 1998-09-15
NO175543B (en) 1994-07-18
EP0668806A1 (en) 1995-08-30
NO924442L (en) 1994-05-19
JPH08502554A (en) 1996-03-19

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