Calcium-lead alloys

Lead—Calcium—Aluminum Alloys. Lead—calcium alloys can be protected against loss of calcium by addition of aluminum. Aluminum provides a protective oxide skin on molten lead—calcium alloys. Even when scrap is remelted, calcium content is maintained by the presence of 0.02 wt % aluminum. Alloys without aluminum rapidly lose calcium, whereas those that contain 0.03 wt % aluminum exhibit negligible calcium losses, as shown in Figure 8 (10). Even with less than optimum aluminum levels, the rate of oxidation is lower than that of aluminum-free alloys. 

Time-weighted average (TWA), 74 215 concentration, 25 372 exposure limit, for tantalum, 24 334 Time-Zero SX-70 film, 79 303, 305-307 Tin (Sn). See Lead-antimony-tin alloys Lead- calcium-tin alloys Lead-lithium-tin alloys Lead-tin alloys, 24 782-800. See also Tin alloys Tin compounds allotropes of, 24 786 analytical methods for, 24 790-792 in antimony alloys, 3 52t atomic structure of, 22 232 in barium alloys, 3 344, 4 12t bismuth recovery from concentrates, 4 5-6... 

Hardening mechanism in lead-calcium alloys. Lead-calcium alloys harden extremely rapidly 80% of the ultimate strength is reached in one day, and virtually full ageing in seven days. Such rapid hardening enhances grid handling and battery production. The rapid hardening was a benefit to VRLA batteries. 

FLAVORCHARACTERIZATION] (Volll) -lead-calcium alloys in READ ALOYS] (Vol 15)... 

FoUowing the removal of the enriched dross, the required quantities of calcium, as a lead—calcium alloy and magnesium in the form of metal ingots, are added. The bath is stirred about 30 min to incorporate the reagents and hasten the reaction. The molten lead is cooled gradually to 380°C to permit the precipitate to grow and soHdify. The dross is skimmed for use with the next lot of lead to be treated. 

Fig. 6. Large columnar as-cast grain stmcture of lead—calcium alloys at a magnification of 80>...

Rea.ctivity ofLea.d—Ca.lcium Alloys. Precise control of the calcium content is required to control the grain stmcture, corrosion resistance, and mechanical properties of lead—calcium alloys. Calcium reacts readily with air and other elements such as antimony, arsenic, and sulfur to produce oxides or intermetaUic compounds (see Calciumand calciumalloys). In these reactions, calcium is lost and suspended soHds reduce fluidity and castibiUty. The very thin grids that are required for automotive batteries are difficult to cast from lead—calcium alloys. 

A rapid method to determine the calcium content of lead alloys is a Hquid-metal titration using lead—antimony (1%) (9). The end point is indicated by a gray oxide film pattern on the surface of a sohdifted sample of the metal when observed at a 45° angle to a light source. The basis for the titration is the reaction between calcium and antimony. The percentage of calcium in the sample can be calculated from the amount of antimony used. If additional calcium is needed in the alloy, the melt is sweetened with a lead—calcium (1 wt %) master alloy. 

Producing lead—calcium—aluminum alloys is difficult. Calcium and aluminum can be added simultaneously to lead using a calcium (73 wt %)—aluminum (27 wt %) master alloy (11) (see Aluminumand aluminum alloys). Using this method, the calcium and aluminum contents can be precisely controlled. Pressed pellets of metallic aluminum andmetaUic calcium are also used. 

Lead—Calcium-Tin Alloys. Tin additions to lead—calcium and lead—calcium—aluminum alloys enhances the mechanical (8) and electrochemical properties (12). Tin additions reduce the rate of aging compared to lead—calcium binary alloys. The positive grid alloys for maintenance-free lead—calcium batteries contain 0.3—1.2 wt % tin and also aluminum. 

Cast lead—calcium—tin alloys usually contain 0.06—0.11 wt % calcium and 0.3 wt % tin. These have excellent fluidity, harden rapidly, have a fine grain stmcture, and are resistant to corrosion. Table 4 Hsts the mechanical properties of cast lead—calcium—tin alloys and other alloys. 

Wrought lead—calcium—tin alloys contain more tin, have higher mechanical strength, exhibit greater stabiUty, and are more creep resistant than the cast alloys. RoUed lead—calcium—tin alloy strip is used to produce automotive battery grids in a continuous process (13). Table 5 Hsts the mechanical properties of roUed lead—calcium—tin alloys, compared with lead—copper and roUed lead—antimony (6 wt %) alloys. 

Lea.dAnodes. A principal use for lead—calcium—tin alloys is lead anodes for electrowinning. The lead—calcium anodes form a hard, adherent lead dioxide layer during use, resist corrosion, and gready reduce lead contamination of the cathode. Anodes produced from cast lead—calcium (0.03—0.09 wt %) alloys have a tendency to warp owing to low mechanical strength and casting defects. 

Wrought lead—calcium—tin anodes have replaced many cast lead—calcium anodes (14). Superior mechanical properties, uniform grain stmcture, low corrosion rates, and lack of casting defects result in increased life for wrought lead—calcium—tin anodes compared to other lead alloy anodes. 

Lead—copper alloys are specified because of superior mechanical properties, creep resistance, corrosion resistance, and high temperature stabiUty compared to pure lead. The mechanical properties of lead—copper alloys are compared to pure lead, and to lead—antimony and lead—calcium alloys in Tables 4 and 5. 

Tia is also used as an ahoyiag element ia lead—antimony alloys to improve fluidity and to prevent drossiag, ia lead—calcium alloys to improve mechanical properties and enhance electrochemical performance, ia lead—arsenic alloys to maintain a stable composition, and as an additive to low melting alloys. 

Sealed batteries have made little entry into this market with heavy cycling service, since the lead-calcium alloys required for these versions tend towards premature capacity loss, a phenomenon intensively investigated in recent years and possibly close to a solution. 

For the separation of such batteries, gel construction and microfiber glass fleece separators again compete because of the deep discharge cycles, the gel construction with its lower tendency to acid stratification and to penetration shorts has advantages for the required power peaks, microfiber glass fleece construction would be the preferred solution. The work on reduction of premature capacity loss with lead-calcium alloys has shown that considerable pressure (e.g., 1 bar) on the positive electrode is able to achieve a significantly better cycle life [31-36], Pressure on the electrodes produces counter pressure on the separators, which is not unproblematic for both separation systems. New separator developments have been presented with... 

The above comparative evaluation of starter battery separators refers to moderate ambient temperatures the standard battery tests arc performed at 40 or 50 °C. What happens, however, on going to significantly higher temperatures, such as 60 or 75 °C This question cannot be answered without considering the alloys used batteries with antimonial alloys show a water consumption that rises steeply with increasing temperature [40], leaving as the only possibilities for such applications either the hybrid construction, i.c., positive electrode with low-antimony alloy, negative electrode lead-calcium, or even both... 

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