US3664831A - Lead alloys having improved corrosion resistance - Google Patents

Lead alloys having improved corrosion resistance Download PDF

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Publication number
US3664831A
US3664831A US20179A US3664831DA US3664831A US 3664831 A US3664831 A US 3664831A US 20179 A US20179 A US 20179A US 3664831D A US3664831D A US 3664831DA US 3664831 A US3664831 A US 3664831A
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United States
Prior art keywords
lead
lead alloys
corrosion resistance
alloys
sulfuric acid
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Expired - Lifetime
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US20179A
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English (en)
Inventor
Hubert Graefen
Dieter Kuron
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BASF SE
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BASF SE
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the range of possible applications of leads and lead alloys available at present is restricted, from the corrosion point of view, by the dissolution of the lead which increases with increasing concentration and increasing temperature of the sulfuric acid.
  • One such limit for the use of lead has hitherto been set by 45% boiling sulfuric acid for example.
  • the range of applications is also restricted, from the point of view of tenacity, by the relatively poor creep resistance of the previously known leads and lead alloys even at only moderately elevated temperatures.
  • the corrosion resistance of lead and lead alloys to sulfuric acid is due to the formation of a protective layer of lead sulfate.
  • a corrosion process must first take place, which is then reduced to a small corrosion rate by the formation of the protective layer of lead sulfate.
  • the formation of a protective layer on pure lead is delayed or completely suppressed.
  • alloying components such as copper or nickel
  • the corrosion of commercially pure lead (Pb 99.985%) and commercial lead alloys (Pb 99.9%, Cu; hard lead 1.5% Sb) by 50% and 70% boiling sulfuric acid solutions is given in Table 1 in mm./year.
  • the magnitude of the hydrogen overpotential of the alloying component is responsible for rapid and effective formation of the protective sulfate layer, but also the size of the cathode area formed, which in turn depends on the solubility and distribution of the alloying component.
  • lead alloys have much greater corrosion resistance, particularly against sulfuric acid, and greatly increased creep resistance when they contain, in addition to alloying components for reducing grain size, assisting the formation of protective layers and increasing creep resistance, such as copper, nickel, tellurium and tin, at elast 0.05%, preferably from 0.1 to 0.2%, of palladium based on the total weight of the alloy.
  • FIG. 1 shows the creep curves of commercially pure lead (Pb 99.985), commercial lead-copper alloy (Pb 99.9 Cu), a lead-copper-palladium alloy according to the invention and a lead-copper-tin-palladium alloy according to the invention.
  • the test temperature is 40 C.
  • the alloys were subjected to loads of 0.6 kg./mm. and 0.4 kg./mm.
  • the Brinell hardness of these alloys, as measured with a ball 2.5 mm. in diameter under a load of 3.1 kg. for a period of 120 seconds is 3.6, 3.6, 4.6 and 6.5 kg./mm. respectively.
  • the samples of pure lead broke under a load of 0.6 kg./mm. after only about 2 hours and under a load of 0.4 kg./mm. after about hours (rupture indicated by x on the curves).
  • the commercial leadcopper alloy (Pb 99.9 Cu) also broke under a load of 0.6 kg./mm.
  • Samples of the lead-copper-palladium alloy did not break when subjected to a load of 0.6 kg./mm. for 700 hours, although the elongation had at his point exceeded 20%.
  • the lead-coppertin-palladium alloy however, showed unexpectedly high creep resistance. After almost 1,000 hours under a load of 0.6 kg./mm. this alloy showed an elongation of only about 2%. Under a load of 0.4 kg./mm. the elongation was less than 1%.
  • the lead alloys of the invention may contain tin in addition to palladium.
  • antimony known from the literature as a method of increasing the tenacity of lead alloys, does not result in the same increase in creep resistance and corrosion resistance as the use of tin as alloying component.
  • FIG. 2 shows the quasistationary anodic current density/potential curves for the two commercial leads (Pb 99.985 and Pb 99.9 Cu) and the two lead alloys of the invention (Pb 99.9 Cu+0.1 Pd and Pb Cu Sn Pd (0.05; 0.12; 0.10)) in boiling 70% sulfuric acid.
  • the current density/potential curves illustrate the two essential effects of the lead alloys of the invention responsible for the increase in corrosion resistance.
  • the steady or corrosion potentials of the lead alloys of the invention have much higher positive values (+500 to +600 mv.), and on the other hand the constant dissolution current density is only about 1X10" amps/cm. as against a value of about 8 l0' for the commercial leads.
  • the main advantages of the lead alloys of the invention over the commercially available leads are their exceptionally high corrosion resistance especially to sulfuric acid and their exceptionally good creep resistance.
  • Lead alloys having improved corrosion resistance, particularly against sulfuric acid, and improved creep resistance which contain, in addition to such alloying components as reduce grain size, assist the formation of protective layers and improve creep resistance, said alloying components selected from the group consisting of copper, nickel, tellurium and tin, a small amount of palladium, which is at least 0.5% based on the total weight of the alloy.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
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US20179A 1969-03-20 1970-03-17 Lead alloys having improved corrosion resistance Expired - Lifetime US3664831A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691914210 DE1914210A1 (https=) 1969-03-20 1969-03-20

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US3664831A true US3664831A (en) 1972-05-23

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US (1) US3664831A (https=)
DE (1) DE1914210A1 (https=)
FR (1) FR2039821A5 (https=)
GB (1) GB1293031A (https=)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808053A (en) * 1971-01-27 1974-04-30 Basf Ag Lead alloy for solid and grid electrodes
US4734256A (en) * 1986-04-21 1988-03-29 Allied-Signal Inc. Wetting of low melting temperature solders by surface active additions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808053A (en) * 1971-01-27 1974-04-30 Basf Ag Lead alloy for solid and grid electrodes
US4734256A (en) * 1986-04-21 1988-03-29 Allied-Signal Inc. Wetting of low melting temperature solders by surface active additions

Also Published As

Publication number Publication date
DE1914210B2 (https=) 1970-06-18
GB1293031A (en) 1972-10-18
FR2039821A5 (https=) 1971-01-15
DE1914210A1 (https=) 1970-06-18

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