Heat Treating of Lead and Lead Alloys

Abstract:

Lead is normally considered to be unresponsive to heat treatment. Yet, some means of strengthening lead and lead alloys may be required for certain applications. Lead alloys for battery components, for example, can benefit from improved creep resistance in order to retain dimensional tolerances for the full service life. Battery grids also require improved hardness to withstand industrial handling.

Lead is normally considered to be unresponsive to heat treatment. Yet, some means of strengthening lead and lead alloys may be required for certain applications. Lead alloys for battery components, for example, can benefit from improved creep resistance in order to retain dimensional tolerances for the full service life. Battery grids also require improved hardness to withstand industrial handling.

The absolute melting point of lead is 327.4°C (621.3°F). Therefore, in applications in which lead is used, recovery and recrystallization processes and creep properties have great significance. Attempts to strengthen the metal by reducing the grain size or by cold working (strain hardening) have proved unsuccessful. Lead-tin alloys, for example, may recrystailize immediately and completely at room temperature. Lead-silver alloys respond in the same manner within two weeks.

Transformations that are induced in steel by heat treatment do not occur in lead alloys, and strengthening by ordering phenomena, such as in the formation of lattice superstructures, has no practical significance.

Despite these obstacles, however, attempts to strengthen lead have had some success.

Solid-Solution Hardening

In solid-solution hardening of lead alloys, the rate of increase in hardness generally improves as the difference between the atomic radius of the solute and the atomic radius of lead increases.

Specifically, in one study of possible binary lead alloys it was found that the following elements, in the order listed, provided successively greater amounts of solid-solution hardening: thallium, bismuth, tin, cadmium, antimony, lithium, arsenic, calcium, zinc, copper, and barium.

Unfortunately, these elements have successively decreasing solid-solution solubilities, and therefore the most potent solutes have the most limited solid-solution hardening effects. Within the midrange of this series, however, are elements that, when alloyed with lead, produce useful strengthening.

A useful level of strengthening normally requires solute additions in excess of the room-temperature solubility limit. In most lead alloys, homogenization and rapid cooling result in a breakdown of the supersaturated solution during storage. Although this breakdown produces coarse structures in certain alloys (lead-tin alloys, for example), it produces fine structures in others (such as lead-antimony alloys). In alloys of the lead-tin system, the initial hardening produced by alloying is quickly followed by softening as the coarse structure is formed.

At suitable solute concentrations in lead-antimony alloys, the structure may remain single phase with hardening by Guinier-Preston (GP) zones formed during aging. At higher concentrations, and in certain other systems, aging may produce precipitation hardening as discrete second-phase particles are formed.

Alloys that exhibit precipitation hardening typically are less susceptible to over aging and therefore are more stable with time than alloys hardened by GP zones. Lead-calcium and lead-strontium alloys have been observed to age harden through discontinuous precipitation of a second phase Pb-Ca and Pb-Sr in lead-strontium alloys as grain boundaries move through the structure.

Solution Treating and Aging

Adding sufficient quantities of antimony to produce hypoeutectic lead-antimony alloys can attain useful strengthening of lead. Small amounts of arsenic have particularly strong effects on the age-hardening response of such alloys, and solution treating and rapid quenching prior to aging enhance these effects.

Hardness Stability. For most of the two-year period, the solution-treated specimens were harder than the quench-east specimens. Other investigations have also shown that alloys cooled slowly after casting are always softer than quenched alloys. The alloys with 2 and 4% Sb harden comparatively slowly, and the alloy containing 6% Sb appears to undergo optimum hardening.

Application. Because of the detrimental effect of antimony on charge retention, the effort to reduce antimony contents of the positive plates in lead-acid storage batteries has led to the trend of replacing eutectic alloys with a Pb-6Sb-0.15As alloy. Battery grids made of this arsenical alloy will age harden slowly after casting and air-cooling. However, storing grids for several days constitutes unproductive use of floor space and results in undesirable interruptions in manufacturing sequences.

Although large-scale solution treatment of battery grids might be difficult to justify economically or to achieve without some distortion, quenching of grids cast from arsenical lead-antimony alloys offers an attractive alternative method of effecting improvements in strength. The suitability of quenched grids can be assessed by comparing with the hardness level that battery grids require in order to withstand industrial handling (about 18 HV, the hardness of the eutectic alloy). The alloy containing 2% Sb clearly does not respond sufficiently to be considered as a possible alternative. The 4% Sb alloy, however, attains a hardness of 18 HV after 30 min, and the alloys that contain 6, 8, and 10% Sb could be handled almost immediately.

Dispersion Hardening

Another mechanism for strengthening of lead alloys involves elements that have low solubilities in solid lead, such as copper and nickel. Alloys that contain these elements can be processed so that no homogenization results; most of the strengthening that occurs is developed through dispersion hardening, with some solid-solution hardening taking place as a secondary effect.

The resulting structure is more stable than those developed by other hardening processes. Dispersion strengthening also has been achieved through powder metallurgy methods in which lead oxide, alumina, or similar materials are dispersed in pure lead.

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