EP0075350A1 - Alloy for inoculating tin-base alloys - Google Patents

Alloy for inoculating tin-base alloys Download PDF

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Publication number
EP0075350A1
EP0075350A1 EP82201099A EP82201099A EP0075350A1 EP 0075350 A1 EP0075350 A1 EP 0075350A1 EP 82201099 A EP82201099 A EP 82201099A EP 82201099 A EP82201099 A EP 82201099A EP 0075350 A1 EP0075350 A1 EP 0075350A1
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EP
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Prior art keywords
tin
alloy
weight
zinc
magnesium
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Granted
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EP82201099A
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German (de)
French (fr)
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EP0075350B1 (en
Inventor
Hartmut Dipl.-Phys. Sandig
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Billiton Witmetaal BV
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EERSTE NEDERLANDSE WITMETAALFABRIEK BV
EERSTE NL WITMETAALFABRIEK BV
Billiton Witmetaal BV
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Priority to AT82201099T priority Critical patent/ATE14754T1/en
Publication of EP0075350A1 publication Critical patent/EP0075350A1/en
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Publication of EP0075350B1 publication Critical patent/EP0075350B1/en
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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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin

Definitions

  • the invention relates to an alloy for inoculating tin alloys, in particular tin casting alloys, and to a method for inoculating the tin alloys.
  • Tin alloys are used to manufacture tin devices by casting or shaping and are described, for example, in part in DIN 1780.
  • the decisive demands on the part of processing tin alloys for the manufacture of tin devices by casting include good mold filling, flow and good make-up behavior, a reduction in the formation of micro voids as well as smooth and non-porous surfaces of the cast tin devices.
  • Good deformability as a result of high elongation at break with sufficient strength, a high limit drawing ratio, low creasing and a flawless surface of the molded parts produced are important for the production of pressed or deep-drawn tin devices.
  • Particularly troublesome surface defects are deep-drawing parabolas in the form of material separations and micro-cracks in the direction of flow and pressure.
  • the more or less strong occurrence of one or more defects of this type can be derived on the one hand from the specification of non-optimal casting, rolling or further processing conditions on the other hand latent due to the alloy composition.
  • the intermetallic Cu 6 Sn 5 phase can increase significantly, which is precipitated in long needles and rhombuses.
  • This structure which is harder than that of the tin-rich mixed crystal, can lead to strong differences in the deformation resistance in the structure and disrupt the uniform flow of the material during pressing and deep drawing.
  • Draw parabolas are the result, especially when this phase occurs frequently in the form of large needles and rhombuses at discrete points in the structure.
  • the present invention is based on the object, in particular in the case of copper-containing tin alloys, of refining the C U6 Sn 5 phase and in the case of lead and antimony-containing tin alloys of achieving grain refinement by inoculation, without the good mechanical and technological properties of the tin alloys affect.
  • tin inoculation alloy with additions of zinc, aluminum and magnesium, so that in the inoculated and to be processed tin alloys 0.0045 to 0.45% by weight, preferably 0.0045 to 0.24% by weight of zinc , 0.0005 to 0.05 wt .-% aluminum and 0.0001 to 0.01 wt .-% magnesium are included.
  • the tin vaccine alloy consists of 6 to 12% by weight zinc, 0.1 to 1% by weight aluminum, 0.008 to 0.8% by weight magnesium, the rest tin.
  • a preferred composition of the tin vaccine alloy consists of 9.25% by weight zinc, 0.5% by weight aluminum, 0.25% by weight magnesium, the rest tin.
  • the method for inoculating tin alloys with the tin inoculation alloy according to the invention is carried out in such a way that it is based on the molten tin alloy to be processed at a temperature of 300 to 400 ° C. in an amount of 0.1 to 1% by weight Amount of the tin alloy melt is added.
  • the tin inoculation alloy can be shot into the tin alloy or stirred into the tin alloy melt while the casting mold is being filled.
  • Grain refinement is achieved by adding the tin inoculation alloy to tin alloys in such a way that the Cu6Sn5 phase is finely dispersed in the direction of globular solidification and that grain refinement is also achieved in tin alloys containing lead and antimony. This results in an improvement in the casting and solidification behavior with regard to improved water make-up, reduction of micro-voids and internal porosity as well as a smoother surface of the cast parts.
  • FIG. 2 shows a metallic micrograph of the tin casting alloy mentioned in FIG. 1, but which has been inoculated with a tin alloy with 8.47% by weight of zinc, 0.47% by weight of aluminum and 0.19% by weight of magnesium so that the tin casting alloy has a zinc content of 0.0360% by weight, an aluminum content of 0.0010% by weight and a magnesium content of 0.00065% by weight.
  • a comparative comparison of the two metallographic micrographs shows that the Cu6Sn5 phase is finely dispersed by adding the tin seed alloy to a conventional tin casting alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Contacts (AREA)
  • Continuous Casting (AREA)

Abstract

1. An inoculating tin alloy for use in making tin alloys, particularly cast tin alloys, which contain 0,004 5 to 0,45 wt.%, preferably 0,004 5 to 0,24 wt.% zinc, 0,000 5 to 0,05 wt.% aluminium and 0,000 1 to 0,01 wt.% magnesium, characterized in that it consists of 6 to 12 wt.% zinc, 0,1 to 1,0 wt.% aluminium, 0,08 to 0,8 wt.% magnesium, balance tin.

Description

Die Erfindung betrifft eine Legierung zum Impfen von Zinnlegierungen,insbesondere Zinngußlegierungen sowie ein Verfahren zum Impfen der Zinnlegierungen.The invention relates to an alloy for inoculating tin alloys, in particular tin casting alloys, and to a method for inoculating the tin alloys.

Zinnlegierungen dienen zur Herstellung von Zinngeräten durch Gießen oder Verformen und sind beispielsweise zum Teil in DIN 1780 beschrieben.Zu den entscheidenen Forderungen von seiten der Verarbeitung an Zinnlegierungen für die Herstellung von Zinngeräten durch Gießen zählen ein gutes Formfüllungs-, Fließ- und ein gutes Nachspeisungsverhalten, eine Reduzierung der Mikrolunkerbildung sowie glatte und porenfreie Oberflächen der gegossenen Zinngeräte. Für die Herstellung von gedrücktem oder tiefgezogenem Zinngerät sind eine gute Verformbarkeit als Folge hoher Bruchdehnung bei ausreichender Festigkeit, ein hohes Grenzziehverhältnis, eine geringe Zipfligkeit und eine fehlerfreie Oberfläche der erzeugten Formteile von Bedeutung. Besonders störende Oberflächenfehler sind Tiefziehparabeln in Form von Materialtrennungen und Mikrorisse in Fließ- und Drückrichtung. Das mehr oder wenige starke Auftreten einer oder mehrerer Fehler dieser Art kann einerseits aus der Vorgabe nicht optimaler Gieß-, Walz- oder Weiterverarbeitungsbedingungen hergeleitet werden, ist andererseits latent durch die Legierungszusammensetzung bedingt. So kann es je nach Vorgabe der Gießbedingungen und der Legierungszusammensetzung zu starken Steigerungen der intermetallischen Cu6Sn5-Phase kommen, die sich in langen Nadeln und Rhomben ausscheidet. Diese gegenüber dem aus dem zinnreichen Mischkristall bestehenden Grundgefüge härterer Phase kann zu starken Unterschieden in den Verformungswiderständen im Gefüge führen und das gleichmäßige Fließen des Werkstoffs beim Drücken und Tiefziehen stören. Ziehparabeln sind die Folge, insbesondere dann, wenn diese Phase an diskreten Stellen im Gefüge gehäuft in Form von großen Nadeln und Rhomben auftritt.Tin alloys are used to manufacture tin devices by casting or shaping and are described, for example, in part in DIN 1780. The decisive demands on the part of processing tin alloys for the manufacture of tin devices by casting include good mold filling, flow and good make-up behavior, a reduction in the formation of micro voids as well as smooth and non-porous surfaces of the cast tin devices. Good deformability as a result of high elongation at break with sufficient strength, a high limit drawing ratio, low creasing and a flawless surface of the molded parts produced are important for the production of pressed or deep-drawn tin devices. Particularly troublesome surface defects are deep-drawing parabolas in the form of material separations and micro-cracks in the direction of flow and pressure. The more or less strong occurrence of one or more defects of this type can be derived on the one hand from the specification of non-optimal casting, rolling or further processing conditions on the other hand latent due to the alloy composition. Depending on the requirements of the casting conditions and the composition of the alloy, the intermetallic Cu 6 Sn 5 phase can increase significantly, which is precipitated in long needles and rhombuses. This structure, which is harder than that of the tin-rich mixed crystal, can lead to strong differences in the deformation resistance in the structure and disrupt the uniform flow of the material during pressing and deep drawing. Draw parabolas are the result, especially when this phase occurs frequently in the form of large needles and rhombuses at discrete points in the structure.

Ausgehend von dieser Erkenntnis liegt der vorliegenden Erfindung die Aufgabe zugrunde, insbesondere bei kupferhaltigen Zinnlegierungen eine Feinung der CU6Sn5-Phase und bei blei- und antimonhaltigen Zinnlegierungen eine Kornfeinung durch Impfen zu erzielen, ohne dabei die guten mechanisch-technologischen Eigenschaften der Zinnlegierungen zu beeinträchtigen.On the basis of this knowledge, the present invention is based on the object, in particular in the case of copper-containing tin alloys, of refining the C U6 Sn 5 phase and in the case of lead and antimony-containing tin alloys of achieving grain refinement by inoculation, without the good mechanical and technological properties of the tin alloys affect.

Gelöst ist diese Aufgabe durch eine Zinnimpflegierung mit Zusätzen von Zink, Aluminium und Magnesium, so daß in den geimpften und zu verarbeitenden Zinnlegierungen 0,0045 bis 0,45 Gew.-%, vorzugsweise 0,0045 bis 0,24 Gew.-% Zink, 0,0005 bis 0,05 Gew.-% Aluminium und 0,0001 bis 0,01 Gew.-% Magnesium enthalten sind.This object is achieved by a tin inoculation alloy with additions of zinc, aluminum and magnesium, so that in the inoculated and to be processed tin alloys 0.0045 to 0.45% by weight, preferably 0.0045 to 0.24% by weight of zinc , 0.0005 to 0.05 wt .-% aluminum and 0.0001 to 0.01 wt .-% magnesium are included.

Insbesondere besteht die Zinnimpflegierung aus 6 bis 12 Gew.-% Zink, 0,1 bis 1 Gew.-% Aluminium, 0,008 bis 0,8 Gew.-% Magnesium, Rest Zinn.In particular, the tin vaccine alloy consists of 6 to 12% by weight zinc, 0.1 to 1% by weight aluminum, 0.008 to 0.8% by weight magnesium, the rest tin.

Eine vorzugsweise Zusammensetzung der Zinnimpflegierung besteht aus 9,25 Gew.-% Zink, 0,5 Gew.-% Aluminium, 0,25 Gew.-% Magnesium, Rest Zinn.A preferred composition of the tin vaccine alloy consists of 9.25% by weight zinc, 0.5% by weight aluminum, 0.25% by weight magnesium, the rest tin.

Das Verfahren zum Impfen von Zinnlegierungen mit der erfindungsgemäßen Zinnimpflegierung wird in der Weise durchgeführt, daß diese in die zu verarbeitende geschmolzene Zinnlegierung bei einer Temperatur von 300 bis 400 °C in einer Menge von 0,1 bis 1 Gew.-% bezogen, auf die Menge der Zinnlegierungsschmelze, zugesetzt wird.The method for inoculating tin alloys with the tin inoculation alloy according to the invention is carried out in such a way that it is based on the molten tin alloy to be processed at a temperature of 300 to 400 ° C. in an amount of 0.1 to 1% by weight Amount of the tin alloy melt is added.

Die Zinnimpflegierung kann während des Füllens der Gießform in die Zinnlegierung eingeschossen oder in die Zinnlegierungsschmelze eingerührt werden.The tin inoculation alloy can be shot into the tin alloy or stirred into the tin alloy melt while the casting mold is being filled.

Gegebenenfalls ist es auch möglich, die Zinnimpflegierung in einer kleinen Schmelzmenge der Zinnlegierung aufzulösen und dann der zu impfenden Zinnschmelze zuzusetzen.If necessary, it is also possible to dissolve the tin inoculation alloy in a small amount of the tin alloy and then add it to the tin melt to be inoculated.

Durch den Zusatz der Zinnimpflegierung zu Zinnlegierungen wird eine Kornfeinung dergestalt erreicht, daß die Cu6Sn5-Phase feindispers in Richtung globulitischer Erstarrung verteilt ist und daß bei blei- und antimonhaltigen Zinnlegierungen ebenfalls eine Kornfeinung erreicht wird. Dadurch eribt sich eine Verbesserung des Guß- und Erstarrungsverhaltens bezüglich verbesserter Nachspeisung, Reduzierung von Mikrolunkerbildung und Innenporosität sowie glatterer Oberfläche der gegossenen Teile.Grain refinement is achieved by adding the tin inoculation alloy to tin alloys in such a way that the Cu6Sn5 phase is finely dispersed in the direction of globular solidification and that grain refinement is also achieved in tin alloys containing lead and antimony. This results in an improvement in the casting and solidification behavior with regard to improved water make-up, reduction of micro-voids and internal porosity as well as a smoother surface of the cast parts.

Die mit der Erfindung erzielten Vorteile sind an Hand der in den Zeichnungen wiedergegebenen metallographischen Gefügeaufnahmen beispielhaft dargestellt und nachfolgend näher erläutert.The advantages achieved with the invention are illustrated by way of example on the basis of the metallographic micrographs shown in the drawings and are explained in more detail below.

Fig 1 zeigt eine metallographische Gefügeaufnahme einer Zinngußlegierung mit 3,02 Gew.-% Antimon, 2,80 Gew.-% Kupfer und 0.043 Gew.-% Blei,wobei die helle Phase die Cu6Sn 5-Phase darstellt.1 shows a metallographic micrograph of a tin casting alloy with 3.02% by weight of antimony, 2.80% by weight of copper and 0.043% by weight of lead, the bright phase representing the Cu 6 Sn 5 phase.

In Fig.2 ist eine metallische Gefügeaufnahme der bei Fig.l genannten Zinngußlegierung wiedergegeben, die jedoch mit einer Zinnlegierung mit 8,47 Gew.-% Zink, 0,47 Gew.-% Aluminium und 0,19 Gew.-% Magnesium geimpft worden ist, so daß sich in der Zinngußlegierung ein Zinkgehalt von 0,0360 Gew.-%, ein Aluminiumgehalt von 0,0010 Gew.-% und ein Magnesiumgehalt von 0,00065 Gew.-% eingestellt hat.2 shows a metallic micrograph of the tin casting alloy mentioned in FIG. 1, but which has been inoculated with a tin alloy with 8.47% by weight of zinc, 0.47% by weight of aluminum and 0.19% by weight of magnesium so that the tin casting alloy has a zinc content of 0.0360% by weight, an aluminum content of 0.0010% by weight and a magnesium content of 0.00065% by weight.

Eine vergleichende Gegenüberstellung der beiden metallographischen Gefügeaufnahmen zeigt, daß durch die Zugabe der Zinnimpflegierung zu einer herkömmlichen Zinngußlegierung die Cu6Sn5-Phase feindispers verteilt ist.A comparative comparison of the two metallographic micrographs shows that the Cu6Sn5 phase is finely dispersed by adding the tin seed alloy to a conventional tin casting alloy.

Claims (8)

1. Legierung zum Impfen von Zinnlegierungen, insbesondere Zinngußlegierungen gekennzeichnet durch eine Zinnimpflegierung mit solchen Gehalten an Zink, Aluminium und Magnesium, daß in der geimpften Zinnlegierung 0,0045 bis 0,45 Gew.-% Zink, 0,0005 bis 0,05 Gew.-% Aluminium und 0,0001 bis 0,01 Gew.-% Magnesium enthalten sind.1. alloy for inoculating tin alloys, in particular tin casting alloys characterized by a tin inoculation alloy with such contents of zinc, aluminum and magnesium that in the inoculated tin alloy 0.0045 to 0.45% by weight zinc, 0.0005 to 0.05% by weight .-% aluminum and 0.0001 to 0.01 wt .-% magnesium are included. 2. Legierung nach Anspruch 1 dadurch gekennzeichnet, daß die Zinkgehalte in der geimpften Zinnlegierung 0,0045 bis 0,24 Gew.-% betragen.2. Alloy according to claim 1, characterized in that the zinc contents in the inoculated tin alloy amount to 0.0045 to 0.24% by weight. 3. Legierung nach den Ansprüchen 1 und 2 dadurch gekennzeichnet, daß sie aus 6 bis 12 Gew.-% Zink, 0,1 bis 1 Gew.- % Aluminium, 0,08 bis 0,8 Gew.- % Magnesium, Rest Zinn besteht.3. Alloy according to claims 1 and 2, characterized in that it consists of 6 to 12 wt .-% zinc, 0.1 to 1 wt .-% aluminum, 0.08 to 0.8 wt .-% magnesium, balance tin consists. 4. Legierung nach den Ansprüchen 1 - 3, dadurch gekennzeichnet, daß sie aus 9,25 Gew.-% Zink, 0,5 Gew.-% Aluminium, 0,25 Gew.-% Magnesium, Rest Zinn besteht.4. Alloy according to claims 1-3, characterized in that it consists of 9.25% by weight zinc, 0.5% by weight aluminum, 0.25% by weight magnesium, the rest tin. 5. Verfahren zum Impfen von Zinngußlegierungen mit der Zinnlegierung nach Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß diese in einer Menge von 0.1 bis 1 Gew.-% bezogen auf die Menge der Zinnlegierungsschmelze dieser bei einer Temperatur von 300 bis 400 °C zugesetzt wird.5. A method for inoculating tin casting alloys with the tin alloy according to claims 1 to 4, characterized in that it is added in an amount of 0.1 to 1 wt .-% based on the amount of the tin alloy melt at a temperature of 300 to 400 ° C. . 6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Zinnimpflegierung während des Füllens der Gießform in die Zinnlegierung eingeschossen wird.6. The method according to claim 5, characterized in that the tin vaccine alloy is shot into the tin alloy during the filling of the casting mold. 7. Verfahren nach Anspruchen 5, dadurch gekennzeichnet, daß die Zinnimpflegierung in die Zinnlegierungsschmelze eingerührt wird.7. The method according to claims 5, characterized in that the tin vaccine alloy is stirred into the tin alloy melt. 8. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Zinnimpflegierung in einer kleinen Schmelzemenge der Zinnlegierung aufgelöst und dann der Zinnlegierungsschmelze zugesetzt wird.8. The method according to claim 5, characterized in that the tin seed alloy is dissolved in a small amount of melt of the tin alloy and then added to the tin alloy melt.
EP82201099A 1981-09-10 1982-09-07 Alloy for inoculating tin-base alloys Expired EP0075350B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82201099T ATE14754T1 (en) 1981-09-10 1982-09-07 ALLOY FOR INOCULATION OF TIN ALLOYS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3135847A DE3135847C2 (en) 1981-09-10 1981-09-10 Master alloy for the production of fine-grain tin alloys
DE3135847 1981-09-10

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EP0075350A1 true EP0075350A1 (en) 1983-03-30
EP0075350B1 EP0075350B1 (en) 1985-08-07

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2589379A1 (en) * 1985-11-05 1987-05-07 Asturienne France Composition for welding or brazing, in particular for assembling zinc elements
WO1998032886A1 (en) * 1997-01-29 1998-07-30 Alpha Fry Limited Lead-free tin alloy
EP1531024A1 (en) * 2002-08-23 2005-05-18 Nippon Metal Industry Co.,Ltd. Tin-zinc lead-free solder, its mixture, and solder-joined part
EP1531025A1 (en) * 2002-08-23 2005-05-18 Nippon Metal Industry Co.,Ltd. Tin-zinc lead-free solder and solder-joined part
CN103831543A (en) * 2012-11-23 2014-06-04 吴永恒 Lead-free soldering material and preparing method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19538365A1 (en) * 1995-10-14 1997-04-17 Leybold Materials Gmbh High purity tin@ alloy target material for sputter coating process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2713196A1 (en) * 1977-03-25 1978-10-05 Ver Zinkwerke Gmbh Alloy contg. tin with antimony and copper - with zinc, aluminium and magnesium additions to improve workability

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2713196A1 (en) * 1977-03-25 1978-10-05 Ver Zinkwerke Gmbh Alloy contg. tin with antimony and copper - with zinc, aluminium and magnesium additions to improve workability

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2589379A1 (en) * 1985-11-05 1987-05-07 Asturienne France Composition for welding or brazing, in particular for assembling zinc elements
WO1998032886A1 (en) * 1997-01-29 1998-07-30 Alpha Fry Limited Lead-free tin alloy
EP1531024A1 (en) * 2002-08-23 2005-05-18 Nippon Metal Industry Co.,Ltd. Tin-zinc lead-free solder, its mixture, and solder-joined part
EP1531025A1 (en) * 2002-08-23 2005-05-18 Nippon Metal Industry Co.,Ltd. Tin-zinc lead-free solder and solder-joined part
EP1531024A4 (en) * 2002-08-23 2006-04-26 Nippon Metal Ind Tin-zinc lead-free solder, its mixture, and solder-joined part
EP1531025A4 (en) * 2002-08-23 2006-04-26 Nippon Metal Ind Tin-zinc lead-free solder and solder-joined part
CN103831543A (en) * 2012-11-23 2014-06-04 吴永恒 Lead-free soldering material and preparing method thereof
CN103831543B (en) * 2012-11-23 2016-08-24 吴永恒 Leadless welding material and preparation method thereof

Also Published As

Publication number Publication date
DE3135847A1 (en) 1983-04-07
DE3265239D1 (en) 1985-09-12
EP0075350B1 (en) 1985-08-07
DE3135847C2 (en) 1983-11-03
ATE14754T1 (en) 1985-08-15

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