EP0019945A1 - Kalzium- und Magnesiumhaltige Bleilegierung - Google Patents

Kalzium- und Magnesiumhaltige Bleilegierung Download PDF

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Publication number
EP0019945A1
EP0019945A1 EP80200322A EP80200322A EP0019945A1 EP 0019945 A1 EP0019945 A1 EP 0019945A1 EP 80200322 A EP80200322 A EP 80200322A EP 80200322 A EP80200322 A EP 80200322A EP 0019945 A1 EP0019945 A1 EP 0019945A1
Authority
EP
European Patent Office
Prior art keywords
magnesium
lead
calcium
strontium
ppm
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.)
Granted
Application number
EP80200322A
Other languages
English (en)
French (fr)
Other versions
EP0019945B1 (de
Inventor
Diederich Jan Baan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to AT80200322T priority Critical patent/ATE15232T1/de
Publication of EP0019945A1 publication Critical patent/EP0019945A1/de
Application granted granted Critical
Publication of EP0019945B1 publication Critical patent/EP0019945B1/de
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C22C11/02—Alloys based on lead with an alkali or an alkaline earth metal as the next major constituent
    • 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

Definitions

  • the invention relates to a process for the preparation of lead containing 100-900 ppm calcium and/or an equivalent amount of strontium in which the calcium and/or strontium is added to a lead melt in elemental form, as a compound and/or as an alloy.
  • the main application of calcium-containing lead and of strontium-containing lead is in the form of battery lead. Further, it finds application as cable lead and as anode material in the zinc electrolysis process.
  • Calcium-and/or strontium-containing lead is usually prepared by melting a lead with a purity of more than 99.9% and by subsequently adding the required alloying elements to the lead melt. This alloying step serves to impart to the lead the desired mechanical properties for battery plates and grids and any other products and also to improve the castability of the lead.
  • antimony In the past antimony was usually added to the lead. However, antimony causes self-discharge in batteries and it was therefore suggested to replace the antimony by calcium and/or strontium, a change which has met with success. In addition, some tin is often added to the melt and it is also possible to add other desired alloying elements. After the addition of the alloying elements, the molten lead is either made into a half-product or cast directly into the desired end-product.
  • a half-product may consist of ingots which are remelted by the battery manufacturer and are further processed into plates and grids. The half-product may also consist of strip produced by continuous casting and/or rolling, which is further processed into plates or grids by the battery manufacturer.
  • the molten lead is in contact with the air.
  • the calcium or strontium content of the melt is found to decrease gradually by oxidation of calcium or strontium, which passes as oxide into the slag layer on top of the melt. Since a certain calcium or strontium content in battery lead is desirable, the diminishing content is found to be very inconvenient. Strontium would usually be required in percentages sufficient to arrive at the desired mechanical properties of the lead and this would normally be less than 2% strontium. It could be partially or totally replaced by calcium of which the influence on the mechanical properties of lead is different. The desired calcium content when calcium is used without any strontium is usually the maximum percentage of calcium soluble in liquid lead at the eutectic temperature (326°C).
  • the present invention proposes to add such an amount of magnesium to the lead melt that less than 100 ppm magnesium is present in the solid lead as prepared. It was surprisingly found that even very low percentages of magnesium in a calcium- or strontium-containing lead melt almost completely inhibit the burning-off of that calcium or strontium. So far no unequivocal explanation for this phenomenon has been found. It is not or at any rate not largely so that the magnesium is sacrificed for the calcium or strontium since in order to prevent a certain quantity of calcium or strontium from being burnt off in a certain period, not a stoichiometric quantity of magnesium is required but a considerably smaller quantity of magnesium is sufficient.
  • the maximum solubility of calcium in liquid lead at the eutectic temperature (326°C) is 800 ppm. According to the invention less than 900 ppm of calcium are therefore added while moreover it is preferred to add approx. 700 ppm of calcium-,... As the result of the magnesium addition it is now sufficient to add the quantity of calcium and/or strontium finally required in the lead.
  • strontium is used instead of calcium in the lead - less than 2% strontium would normally be required.
  • both the calcium and/or strontium and the magnesium can-be, added in elemental form, in the form of a compound or as an alloy.
  • the percentages given in this specification are all percentages by weight and, where the relevant metal is added in the bound form, they relate to the proportion of that same metal.
  • difficulties may be experienced in the addition of the additives to the melt, for example because of the density of the additive (it may float on the lead melt), because of the melting point of the additive (at low melting points fewer difficulties will occur than at higher melting points) or because of the rate at which the additive dissolves in the melt.
  • magnesium in the form of a preliminary alloy or in the form of an intermetallic compound, for example with lead (high density), with aluminium (low melting point) or with calcium or strontium (the problem is halved since only one further additive is required).
  • magnesium-aluminium alloy it is preferred to select an alloy containing 30-70% of magnesium, since these alloys have a melting point near the usual temperature of a lead melt.
  • An advantage of adding a magnesium-calcium alloy or a magnesium-strontium alloy instead of a magnesium-aluminium alloy is that the corrosion resistance of lead containing magnesium is distinctly higher than that of lead containing an equal quantity of aluminium. Besides, magnesium dissolves in liquid lead more readily than aluminium.
  • the invention is eminently suitable for those leads which contain tin (usually less than 1%), since tin accelerates the burning-off of calcium-containing lead in a melt, so that in this instance the addition of magnesium is all the more essential.
  • the exclusive right also pertains to lead obtained with the process according to the invention and to battery plates or grids produced from a lead melt which is obtained in accordance with the invention.
  • the calcium content was determined with an accuracy of approx. 50 ppm. It can be seen from Table 1 that the calcium content of a melt without magnesium declines rapidly and that addition of magnesium produces a change.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Fittings On The Vehicle Exterior For Carrying Loads, And Devices For Holding Or Mounting Articles (AREA)
  • Emergency Alarm Devices (AREA)
EP80200322A 1979-05-14 1980-04-11 Kalzium- und Magnesiumhaltige Bleilegierung Expired EP0019945B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80200322T ATE15232T1 (de) 1979-05-14 1980-04-11 Kalzium- und magnesiumhaltige bleilegierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL7903764 1979-05-14
NL7903764A NL7903764A (nl) 1979-05-14 1979-05-14 Werkwijze ter bereiding van calcium-houdend lood, daarmee verkregen lood en daaruit verkregen accuplaten of -roosters.

Publications (2)

Publication Number Publication Date
EP0019945A1 true EP0019945A1 (de) 1980-12-10
EP0019945B1 EP0019945B1 (de) 1985-08-28

Family

ID=19833175

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80200322A Expired EP0019945B1 (de) 1979-05-14 1980-04-11 Kalzium- und Magnesiumhaltige Bleilegierung

Country Status (6)

Country Link
EP (1) EP0019945B1 (de)
JP (1) JPS55152142A (de)
AT (1) ATE15232T1 (de)
DE (1) DE3071027D1 (de)
DK (1) DK156490C (de)
NL (1) NL7903764A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041160A (en) * 1988-05-20 1991-08-20 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
AU620822B2 (en) * 1988-05-20 1992-02-27 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
WO2002071511A3 (en) * 2001-02-06 2004-03-11 Rsr Technologies Inc Method for enhancing lead oxidation during production of lead acid batteries
EP2371383B1 (de) 2005-12-29 2015-08-19 Boehringer Ingelheim Vetmedica, Inc. Verwendung einer immunogenen PCV2-Zusammensetzung zur Abschwächung von Krankheitssymptomen bei Schweinen

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5143693A (en) * 1988-05-20 1992-09-01 Timminco Limited Magnesium-calcium alloys for debismuthizing lead

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE323852C (de) * 1915-07-31 1920-08-10 United Lead Company Bleilegierung
GB499549A (en) * 1937-03-19 1939-01-25 American Smelting Refining Lead alloys
US2306899A (en) * 1942-02-28 1942-12-29 American Smelting Refining Alloy
US3920473A (en) * 1971-12-15 1975-11-18 Lucas Batteries Ltd Battery plate grids for lead-acid batteries
GB1414171A (en) * 1972-02-09 1975-11-19 Lucas Batteries Ltd Battery plate grids for lead-acid batteries and alloys for use in the production of such grids
DE2611575A1 (de) * 1976-03-19 1977-09-29 Metallgesellschaft Ag Blei-calcium-knetlegierung
DE2921290A1 (de) * 1978-05-26 1979-12-06 Chloride Group Ltd Blei-erdalkalimetall-legierung und akkumulator mit traegergeruest hieraus

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1458016A (en) * 1973-06-06 1976-12-08 Lucas Batteries Ltd Manufacture of ternary alloys of lead calcium and aluminium

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE323852C (de) * 1915-07-31 1920-08-10 United Lead Company Bleilegierung
GB499549A (en) * 1937-03-19 1939-01-25 American Smelting Refining Lead alloys
US2306899A (en) * 1942-02-28 1942-12-29 American Smelting Refining Alloy
US3920473A (en) * 1971-12-15 1975-11-18 Lucas Batteries Ltd Battery plate grids for lead-acid batteries
GB1414171A (en) * 1972-02-09 1975-11-19 Lucas Batteries Ltd Battery plate grids for lead-acid batteries and alloys for use in the production of such grids
DE2611575A1 (de) * 1976-03-19 1977-09-29 Metallgesellschaft Ag Blei-calcium-knetlegierung
DE2921290A1 (de) * 1978-05-26 1979-12-06 Chloride Group Ltd Blei-erdalkalimetall-legierung und akkumulator mit traegergeruest hieraus

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041160A (en) * 1988-05-20 1991-08-20 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
AU620822B2 (en) * 1988-05-20 1992-02-27 Timminco Limited Magnesium-calcium alloys for debismuthizing lead
WO2002071511A3 (en) * 2001-02-06 2004-03-11 Rsr Technologies Inc Method for enhancing lead oxidation during production of lead acid batteries
EP2371383B1 (de) 2005-12-29 2015-08-19 Boehringer Ingelheim Vetmedica, Inc. Verwendung einer immunogenen PCV2-Zusammensetzung zur Abschwächung von Krankheitssymptomen bei Schweinen
EP2371385B1 (de) 2005-12-29 2015-08-19 Boehringer Ingelheim Vetmedica, Inc. Verwendung einer immunogenen PCV2-Zusammensetzung zur Abschwächung von Krankheitssystemen bei Schweinen
EP2371382B1 (de) 2005-12-29 2016-03-02 Boehringer Ingelheim Vetmedica, Inc. Verwendung einer immunogenen PCV2-Zusammensetzung zur Abschwächung von Krankheitssystemen bei Schweinen

Also Published As

Publication number Publication date
JPS55152142A (en) 1980-11-27
JPH0420972B2 (de) 1992-04-07
DK156490C (da) 1990-01-29
ATE15232T1 (de) 1985-09-15
DK150880A (da) 1980-11-15
DK156490B (da) 1989-08-28
DE3071027D1 (en) 1985-10-03
NL7903764A (nl) 1980-11-18
EP0019945B1 (de) 1985-08-28

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