BE1008479A3 - Zinc alloy castable room hot. - Google Patents

Zinc alloy castable room hot. Download PDF

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Publication number
BE1008479A3
BE1008479A3 BE9400676A BE9400676A BE1008479A3 BE 1008479 A3 BE1008479 A3 BE 1008479A3 BE 9400676 A BE9400676 A BE 9400676A BE 9400676 A BE9400676 A BE 9400676A BE 1008479 A3 BE1008479 A3 BE 1008479A3
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Belgium
Prior art keywords
alloy
zinc
alloy according
sep
alloys
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Application number
BE9400676A
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French (fr)
Inventor
Laurent R A G Coster
Didier Rollez
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Union Miniere Sa
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Priority to BE9400676A priority Critical patent/BE1008479A3/en
Application filed by Union Miniere Sa filed Critical Union Miniere Sa
Priority to CA002185013A priority patent/CA2185013C/en
Priority to PL95318133A priority patent/PL178557B1/en
Priority to CZ199751A priority patent/CZ287825B6/en
Priority to DK95926933T priority patent/DK0771365T3/en
Priority to PCT/EP1995/002820 priority patent/WO1996002682A1/en
Priority to JP50471196A priority patent/JP3800345B2/en
Priority to EP95926933A priority patent/EP0771365B1/en
Priority to BR9507577A priority patent/BR9507577A/en
Priority to DE69505820T priority patent/DE69505820T2/en
Priority to ES95926933T priority patent/ES2126301T3/en
Priority to AT95926933T priority patent/ATE173029T1/en
Priority to AU31139/95A priority patent/AU3113995A/en
Priority to KR1019960705161A priority patent/KR100343309B1/en
Priority to PE1995273756A priority patent/PE12696A1/en
Application granted granted Critical
Publication of BE1008479A3 publication Critical patent/BE1008479A3/en
Priority to FI970177A priority patent/FI114400B/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C18/00Alloys based on zinc
    • C22C18/04Alloys based on zinc with aluminium as the next major constituent

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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)
  • Continuous Casting (AREA)
  • Forging (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Ceramic Products (AREA)
  • Ink Jet (AREA)
  • Supercharger (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Adornments (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Conductive Materials (AREA)
  • Mold Materials And Core Materials (AREA)
  • Sliding-Contact Bearings (AREA)
  • Vertical, Hearth, Or Arc Furnaces (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)

Abstract

Alloy containing, in percentage by weight, (a) either 15-20 Al and 8-10 Cu, or 25-30 Al and 15-20 Cu; and (b) 0.01-2 Si, 0-0.1 Mg, 0-0.5 Ti, 0-0.5 Cr, 0-1Mn, 0-0.5 Nb and 0-0.1 of a metal or a mixture of rare earth metals, the remainder being zinc. The alloy has excellent creep and tensile strength, when it contains 15-20 Al and 8-10 Cu weight percent, and excellent creep and tensile strength when it contains 25-30 Al and 15-20 Cu.

Description

       

   <Desc/Clms Page number 1> 
 



   ALLIAGE DE ZINC COULABLE EN CHAMBRE CHAUDE. 



  La présente invention rapporte à un alliage à base de zinc contenant Al et Cu, coulable sous pression dans une machine à chambre chaude. 



  Un tel alliage est décrit dans le   do : ument"SAE technical-per séries   930788. ACuZinc : improved zinc alloys for die casting application, M. D. Hanna and M. S. Rashid. International Congress and Exposition Detroit, Michigan, March 1-5,1993". Cet alliage connu, appelé "ACuZinc   5"est   constitué de 5,0-6, 0% de Cu, 2,8-3, 3%   d'Al   et 0,025- 0,05% de Mg, reste Zn (tous les pourcentages donnés dans la présente demande de brevet sont des % en poids). La résistance au fluage de cet alliage, quoique sensiblement supérieure à celle des alliages Zamak ou ZA coulés depuis longue date en chambre chaude, est encore relativement faible. 



  Le but de la présente invention est de fournir un alliage tel que défini ci-dessus, qui présente une meilleure résistance au fluage que l'alliage connu précité. 



  A cet effet, selon l'invention l'alliage contient 12-30% d'Al, 5-20% de Cu, 0,01-2% de Si, 0-1% de Mg, 0-1% de Ti, 0-0,5% de Cr, 0-1% de Mn, 0-0,5% de Nb et 0-0,1% d'un métal des terres rares tel que Y ou d'un mélange de métaux des terres rares, le reste étant du zinc et les impuretés inévitablement présentes dans le zinc et dans les éléments d'alliage précités. 



  En effet, il a été trouvé d'une part qu'un tel alliage présente à l'état liquide une si faible agressivité vis-à-vis des aciers qu'il est coulable en chambre chaude et d'autre part qu'il présente à l'état coulé une bonne résistance au fluage. 



  L'alliage selon l'invention contient avantageusement 12-20%   d'Al   en combinaison avec 5-13% de Cu ou 25-30%   d'Aï   en combinaison avec 15-20% 
 EMI1.1 
 de Cu, et préférentiellement 15-17% d'Al en combinaison avec 8-10% de Cu ou 25, 5-28, 5% d'Al en combinaison avec 15-18% de Cu. 



  La teneur préférentielle en Si est de 0,1-1%. 



  Il est souhaitable que le Zn, Al et Cu, utilisés pour fabriquer l'alliage, aient une pureté de respectivement      99,995%,      99,97% et    >    99,99%, parce qu'il a été trouvé que la présence dans l'alliage 

 <Desc/Clms Page number 2> 

 d'impuretés influence défavorablement sa fluidité et ses propriétés mécaniques. 



  Lorsque l'alliage contient un métal ayant une très grande affinité pour l'oxygène, tel que par exemple Y, au moins une partie de ce métal peut être orésente à l'état oxydé. 



  L'excellente résistance au fluage de l'alliage selon l'invention est illustrée par la description ci-dessous d'une série d'essais comparatifs, dont les résultats sont donnés dans le diagramme cijoint. 



  On a testé deux alliages connus, Zamak 5 et ACuZinc 5, et deux alliages selon l'invention, qui seront désignés ci-après par"X27"et   "X28",   Composition de ces alliages : - Zamak 5 : 4% Al, 1% Cu, 0,04% Mg, reste Zn ;
ACuZinc 5 : 3% Al, 5,5% Cu, 0,04% Mg, reste   Zn ;   
 EMI2.1 
 X27 : 17% Al, 9, 5% Cu, 0, 5% Si, reste Zn ; X28 : 27% Al, 16, 5% Cu, 0, 1% Si, reste Zn. On a coulé des éprouvettes de ces alliages dans une machine à chambre chaude. 



  Les conditions générales de coulée étaient comme   suit :   temps de cycle : 12 secondes - température du bain :   420-520oC   - pression exercée sur le métal : 50 MPa - vitesse du piston   : 1,   2 m/s - diamètre de buse   : 9,   5 mm - température du moule :   180-2500C   La forme et les dimensions de ces éprouvettes sont celles prescrites par le Comité Technique des Producteurs Européens de Zinc pour les éprouvettes à utiliser dans l'essai de traction des tôles et feuilles en zinc et en alliages de zinc. 



  Les éprouvettes ont été soumises à l'essai de fluage à   100. C   sous une charge de 40   MPa.   Les courbes de fluage, donnant l'allongement (en%) mesuré en fonction du temps (en heures), sont représentées au diagramme ci-joint. 

 <Desc/Clms Page number 3> 

 On voit que les alliages selon l'invention résistent beaucoup mieux au fluage que les alliages connus. 



  Les alliages selon l'invention se distinguent non seulement par leur bonne résistance au fluage, mais encore par leur dureté élevée, comme cela ressort du tableau ci-dessous donnant la dureté à l'état coulé des alliages X27 et X28 et d'une série d'alliages connus. 



   Tableau 
 EMI3.1 
 
<tb> 
<tb> Alliage <SEP> Dureté <SEP> Brinell
<tb> (62,5 <SEP> kgf)
<tb> Zamak <SEP> 3 <SEP> (1) <SEP> 82
<tb> Zamak <SEP> 5 <SEP> 91
<tb> ACuZinc <SEP> 5 <SEP> 119
<tb> ACuZinc <SEP> 10 <SEP> (2) <SEP> 145
<tb> ZA <SEP> 12 <SEP> (3) <SEP> 110
<tb> ZA <SEP> 27 <SEP> (4) <SEP> 115
<tb> X27 <SEP> 149
<tb> X28 <SEP> 185
<tb> 
 (1) 4% Al, 0,001% Cu, 0,04% Mg, reste Zn ; coulable en chambre chaude. 



   (2) 3,5%   Al,   10,5% Cu, 0,04% Mg, reste Zn ; coulable en chambre froide. 



   (3) 4%   Al,   0,85% Cu, 0,022% Mg, reste Zn ; coulable en chambre chaude. 



   (4) 26% Al, 2,5% Cu, 0,015% Mg, reste Zn ; coulable en chambre froide. 



  La présente invention se rapporte également à un procédé de fabrication d'articles en un alliage à base de zinc contenant Al et Cu par coulée sous pression dans une machine à chambre chaude, ce procédé étant caractérisé en ce que l'alliage est l'alliage de l'invention. 



  Comme l'alliage de l'invention est coulable en chambre chaude, il est forcément coulable en chambre froide et en gravité. 



  La présente invention se rapporte donc également à un procédé de fabrication d'articles en un alliage à base de zinc contenant Al et Cu par coulée sous pression dans une machine à chambre froide ou par coulée en gravité, ce procédé étant caractérisé en ce que l'alliage est l'alliage de l'invention. 



  La présente invention se rapporte en outre à l'utilisation de l'alliage selon l'invention comme matériau antifriction.



   <Desc / Clms Page number 1>
 



   CASTABLE ZINC ALLOY IN HOT CHAMBER.



  The present invention relates to a zinc-based alloy containing Al and Cu, which can be cast under pressure in a hot chamber machine.



  Such an alloy is described in the do: ument "SAE technical-per series 930788. ACuZinc: improved zinc alloys for die casting application, M. D. Hanna and M. S. Rashid. International Congress and Exposition Detroit, Michigan, March 1-5.1993". This known alloy, called "ACuZinc 5" consists of 5.0-6.0% Cu, 2.8-3.3% Al and 0.025-0.05% Mg, remains Zn (all percentages given in the present patent application are% by weight). The creep resistance of this alloy, although appreciably greater than that of Zamak or ZA alloys which have been cast for a long time in a hot chamber, is still relatively low.



  The object of the present invention is to provide an alloy as defined above, which has better creep resistance than the known alloy mentioned above.



  To this end, according to the invention, the alloy contains 12-30% Al, 5-20% Cu, 0.01-2% Si, 0-1% Mg, 0-1% Ti, 0-0.5% Cr, 0-1% Mn, 0-0.5% Nb and 0-0.1% of a rare earth metal such as Y or a mixture of earth metals rare, the remainder being zinc and the impurities inevitably present in the zinc and in the abovementioned alloying elements.



  Indeed, it has been found on the one hand that such an alloy has in the liquid state such low aggressiveness with respect to steels that it is pourable in a hot chamber and on the other hand that it has in the cast state, good creep resistance.



  The alloy according to the invention advantageously contains 12-20% Al in combination with 5-13% Cu or 25-30% Al in combination with 15-20%
 EMI1.1
 Cu, and preferably 15-17% Al in combination with 8-10% Cu or 25.5-28.5% Al in combination with 15-18% Cu.



  The preferred Si content is 0.1-1%.



  It is desirable that the Zn, Al and Cu, used to make the alloy, have a purity of 99.995%, 99.97% and> 99.99%, respectively, because it has been found that the presence in the alloy

 <Desc / Clms Page number 2>

 impurities adversely affect its fluidity and mechanical properties.



  When the alloy contains a metal having a very high affinity for oxygen, such as for example Y, at least part of this metal can be present in the oxidized state.



  The excellent creep resistance of the alloy according to the invention is illustrated by the description below of a series of comparative tests, the results of which are given in the attached diagram.



  Two known alloys were tested, Zamak 5 and ACuZinc 5, and two alloys according to the invention, which will be designated below by "X27" and "X28", Composition of these alloys: - Zamak 5: 4% Al, 1 % Cu, 0.04% Mg, residue Zn;
ACuZinc 5: 3% Al, 5.5% Cu, 0.04% Mg, residue Zn;
 EMI2.1
 X27: 17% Al, 9.5% Cu, 0.5% Si, remains Zn; X28: 27% Al, 16.5% Cu, 0.1% Si, remains Zn. Test pieces of these alloys were poured into a hot chamber machine.



  The general casting conditions were as follows: cycle time: 12 seconds - bath temperature: 420-520oC - pressure exerted on the metal: 50 MPa - piston speed: 1, 2 m / s - nozzle diameter: 9, 5 mm - mold temperature: 180-2500C The shape and dimensions of these test pieces are those prescribed by the Technical Committee of European Zinc Producers for the test pieces to be used in the tensile test of sheets and sheets of zinc and alloys zinc.



  The test pieces were subjected to the creep test at 100. C under a load of 40 MPa. The creep curves, giving the elongation (in%) measured as a function of time (in hours), are shown in the attached diagram.

 <Desc / Clms Page number 3>

 It can be seen that the alloys according to the invention resist creep much better than known alloys.



  The alloys according to the invention are distinguished not only by their good creep resistance, but also by their high hardness, as shown in the table below giving the hardness in the cast state of alloys X27 and X28 and of a series of known alloys.



   Board
 EMI3.1
 
<tb>
<tb> Alloy <SEP> Hardness <SEP> Brinell
<tb> (62.5 <SEP> kgf)
<tb> Zamak <SEP> 3 <SEP> (1) <SEP> 82
<tb> Zamak <SEP> 5 <SEP> 91
<tb> ACuZinc <SEP> 5 <SEP> 119
<tb> ACuZinc <SEP> 10 <SEP> (2) <SEP> 145
<tb> ZA <SEP> 12 <SEP> (3) <SEP> 110
<tb> ZA <SEP> 27 <SEP> (4) <SEP> 115
<tb> X27 <SEP> 149
<tb> X28 <SEP> 185
<tb>
 (1) 4% Al, 0.001% Cu, 0.04% Mg, residue Zn; flowable in hot room.



   (2) 3.5% Al, 10.5% Cu, 0.04% Mg, residue Zn; pourable in cold room.



   (3) 4% Al, 0.85% Cu, 0.022% Mg, residue Zn; flowable in hot room.



   (4) 26% Al, 2.5% Cu, 0.015% Mg, residue Zn; pourable in cold room.



  The present invention also relates to a process for manufacturing articles of a zinc-based alloy containing Al and Cu by die-casting in a hot chamber machine, this process being characterized in that the alloy is the alloy of the invention.



  As the alloy of the invention is pourable in a hot room, it is necessarily pourable in a cold room and by gravity.



  The present invention therefore also relates to a process for manufacturing articles of a zinc-based alloy containing Al and Cu by pressure casting in a cold room machine or by gravity casting, this process being characterized in that the alloy is the alloy of the invention.



  The present invention also relates to the use of the alloy according to the invention as an anti-friction material.


    

Claims (9)

REVENDICATIONS 1. Alliage à base de zinc contenant Al et Cu, coulable sous pression dans une machine à chambre chaude, caractérisé en ce qu'il contient 12-30% d'Al, 5-20% de Cu, 0,01-2% de Si, 0-0,1% de Mg, 0-0,5% de Ti, 0-0, 5% de Cr, 0-1% de Mn, 0-0,5% de Nb et 0-0, 1% d'un métal os d'un mélange de métaux des terres rares, le reste étant du zinc et les impuretés inévitablement présentes dans le zinc et les éléments d'alliage précités.  CLAIMS 1. Zinc-based alloy containing Al and Cu, flowable under pressure in a hot chamber machine, characterized in that it contains 12-30% Al, 5-20% Cu, 0.01-2% Si, 0-0.1% Mg, 0-0.5% Ti, 0-0.5% Cr, 0-1% Mn, 0-0.5% Nb and 0-0.1% of a bone metal of a mixture of rare earth metals, the rest being zinc and the impurities inevitably present in the aforementioned zinc and the alloying elements. 2. Alliage selon la revendication 1, caractérisé en ce qu'il contient 12-20% d'Al et 5-13% de Cu. 2. Alloy according to claim 1, characterized in that it contains 12-20% Al and 5-13% Cu. 3. Alliage selon la revendication 2, caractérisé en ce qu'il contient 15-17% Al et 8-10% Cu. 3. Alloy according to claim 2, characterized in that it contains 15-17% Al and 8-10% Cu. 4. Alliage selon la revendication 1, caractérisé en ce qu'il contient 25-30% d'Al et 15-20% de Cu. 4. Alloy according to claim 1, characterized in that it contains 25-30% Al and 15-20% Cu. 5. Alliage selon la revendication 4, caractérisé en ce qu'il contient 25,5-28, 5% Al et 15-18% Cu. 5. Alloy according to claim 4, characterized in that it contains 25.5-28.5% Al and 15-18% Cu. 6. Alliage selon l'une quelconque des revendications 1-5, caractérisé en ce qu'il contient 0,1-1% de Si. 6. Alloy according to any one of claims 1-5, characterized in that it contains 0.1-1% of Si. 7. Alliage selon l'une quelconque des revendications 1-6, caractérisé en ce que Zn, Al et Cu ont une pureté de respectivement 2 99,995%, 2 99,97% et 2 99,99%. 7. Alloy according to any one of claims 1-6, characterized in that Zn, Al and Cu have a purity of 2 99.995% respectively, 2 99.97% and 2 99.99%. 8. Procédé de fabrication d'articles en un alliage à base de zinc contenant Al et Cu par coulée sous pression dans une machine à chambre chaude ou dans une machine à chambre froide ou par coulée en gravité, caractérisé en ce que l'alliage est l'alliage selon les revendications 1-7. 8. A method of manufacturing articles of a zinc-based alloy containing Al and Cu by pressure casting in a hot room machine or in a cold room machine or by gravity casting, characterized in that the alloy is the alloy according to claims 1-7. 9. Utilisation de l'alliage selon les revendications 1-7 comme matériau antifriction. 9. Use of the alloy according to claims 1-7 as an anti-friction material.
BE9400676A 1994-07-18 1994-07-18 Zinc alloy castable room hot. BE1008479A3 (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
BE9400676A BE1008479A3 (en) 1994-07-18 1994-07-18 Zinc alloy castable room hot.
ES95926933T ES2126301T3 (en) 1994-07-18 1995-07-12 ZINC ALLOY MOLDABLE BY CASTING IN A HOT CHAMBER.
CZ199751A CZ287825B6 (en) 1994-07-18 1995-07-12 Alloy based on zinc, process for producing products from such alloy and use of the alloy
DK95926933T DK0771365T3 (en) 1994-07-18 1995-07-12 Zinc alloy for casting in heating chamber
PCT/EP1995/002820 WO1996002682A1 (en) 1994-07-18 1995-07-12 Hot chamber castable zinc alloy
JP50471196A JP3800345B2 (en) 1994-07-18 1995-07-12 Hot chamber castable zinc alloy
CA002185013A CA2185013C (en) 1994-07-18 1995-07-12 Hot chamber castable zinc alloy
BR9507577A BR9507577A (en) 1994-07-18 1995-07-12 Zinc based alloy containing Ap and Cu manufacturing process of articles with this alloy and using it
DE69505820T DE69505820T2 (en) 1994-07-18 1995-07-12 ZINC ALLOY FOR DIE CASTING IN WARM PRINT CHAMBER
PL95318133A PL178557B1 (en) 1994-07-18 1995-07-12 Zinc alloy suitable for hot-chamber casting
AT95926933T ATE173029T1 (en) 1994-07-18 1995-07-12 ZINC ALLOY FOR DIE CASTING IN WARM PRESSURE CHAMBER
AU31139/95A AU3113995A (en) 1994-07-18 1995-07-12 Hot chamber castable zinc alloy
KR1019960705161A KR100343309B1 (en) 1994-07-18 1995-07-12 Hot chamber castable zinc alloy
EP95926933A EP0771365B1 (en) 1994-07-18 1995-07-12 Hot chamber castable zinc alloy
PE1995273756A PE12696A1 (en) 1994-07-18 1995-07-13 DRAINABLE ZINC ALLOY IN HOT CHAMBER
FI970177A FI114400B (en) 1994-07-18 1997-01-16 Zinc alloy cast in hot chamber

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE9400676A BE1008479A3 (en) 1994-07-18 1994-07-18 Zinc alloy castable room hot.

Publications (1)

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BE1008479A3 true BE1008479A3 (en) 1996-05-07

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BE9400676A BE1008479A3 (en) 1994-07-18 1994-07-18 Zinc alloy castable room hot.

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JP (1) JP3800345B2 (en)
KR (1) KR100343309B1 (en)
AT (1) ATE173029T1 (en)
AU (1) AU3113995A (en)
BE (1) BE1008479A3 (en)
BR (1) BR9507577A (en)
CA (1) CA2185013C (en)
CZ (1) CZ287825B6 (en)
DE (1) DE69505820T2 (en)
DK (1) DK0771365T3 (en)
ES (1) ES2126301T3 (en)
FI (1) FI114400B (en)
PE (1) PE12696A1 (en)
PL (1) PL178557B1 (en)
WO (1) WO1996002682A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100961081B1 (en) * 2009-03-03 2010-06-08 임현규 Zinc-aluminium alloys with high strength and low density
KR101955995B1 (en) * 2017-03-21 2019-03-08 주식회사 지.에이.엠 High strength aluminium-zinc alloy and high strength aluminium-zinc alloy casting
CN112522540A (en) * 2020-12-01 2021-03-19 江苏同生特钢制造有限公司 Zinc alloy casting and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB769483A (en) * 1953-06-30 1957-03-06 Willi Neu Zinc aluminium alloy and process for the production thereof
US2870008A (en) * 1954-11-18 1959-01-20 Main Alloy Company Establishme Zinc-aluminium alloys and the method for producing same
US4789522A (en) * 1986-06-27 1988-12-06 Queen's University At Kingston Castable zinc-aluminum alloys

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB769483A (en) * 1953-06-30 1957-03-06 Willi Neu Zinc aluminium alloy and process for the production thereof
US2870008A (en) * 1954-11-18 1959-01-20 Main Alloy Company Establishme Zinc-aluminium alloys and the method for producing same
US4789522A (en) * 1986-06-27 1988-12-06 Queen's University At Kingston Castable zinc-aluminum alloys

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AU3113995A (en) 1996-02-16
FI970177A0 (en) 1997-01-16
FI970177A (en) 1997-01-16
EP0771365A1 (en) 1997-05-07
ES2126301T3 (en) 1999-03-16
KR100343309B1 (en) 2002-11-25
PL178557B1 (en) 2000-05-31
JP3800345B2 (en) 2006-07-26
DE69505820D1 (en) 1998-12-10
CA2185013A1 (en) 1996-02-01
DE69505820T2 (en) 1999-07-08
CZ287825B6 (en) 2001-02-14
CZ5197A3 (en) 1997-04-16
CA2185013C (en) 2006-08-29
PE12696A1 (en) 1996-04-23
ATE173029T1 (en) 1998-11-15
FI114400B (en) 2004-10-15
WO1996002682A1 (en) 1996-02-01
BR9507577A (en) 1997-09-09
PL318133A1 (en) 1997-05-12
DK0771365T3 (en) 1999-07-19
JPH10502705A (en) 1998-03-10
EP0771365B1 (en) 1998-11-04

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