Antimony in lead

A simple, rapid and seleetive eleetroehemieal method is proposed as a novel and powerful analytieal teehnique for the solid phase determination of less than 4% antimony in lead-antimony alloys without any separation and ehemieal pretreatment. The proposed method is based on the surfaee antimony oxidation of Pb/Sb alloy to Sb(III) at the thin oxide layer of PbSOyPbO that is formed by oxidation of Pb and using linear sweep voltammetrie (LSV) teehnique. Determination was earried out in eoneentrate H SO solution. The influenee of reagent eoneentration and variable parameters was studied. The method has deteetion limit of 0.056% and maximum relative standard deviation of 4.26%. This method was applied for the determination of Sb in lead/aeid battery grids satisfaetory. 

Antimony was originaUy chosen as an alloying element because it imparted hardness to the grids, which allowed them to withstand the intense mechanical stresses associated with chemical reactions within the battery itself and with difficult physical conditions, including vibrations and shocks related to on-the-road use. However, since the late 1970s calcium has been increasingly used in place of antimony in lead-alloy grid manufacture, due both to its beneficial impact on battery life, and because it permits low or zero maintenance battery operation. ... 

The above-mentioned solid solution of antimony in lead causes supersaturation when the usual technique of grid casting is applied, because at room temperature the solubility of antimony in lead is extremely low compared to the 3.5% solubility at 252°C. The reduction of supersaturation by precipitation of finely dispersed antimony within the lead-antimony solid solution grains causes the ever-present age-hardening. 

The age-hardening is also increased by further additives, e.g. arsenic. The influence of arsenic is more effective when the supersaturation of antimony in lead is relatively low (e.g. for grids not subjected to special heat treatment). Figure 18.12 shows this effect arsenic not only increases, but also accelerates the agehardening process. 

Reverberator Furnace. Using a reverberatory furnace, a fine particle feed can be used, the antimony content can be controlled, and batch operations can be carried out when the supply of scrap material is limited. However, the antimony-rich slags formed must be reduced in a blast furnace to recover the contained antimony and lead. For treating battery scrap, the reverberatory furnace serves as a large melting faciUty where the metallic components are hquefted and the oxides and sulfate in the filler material are concurrently reduced to lead metal and the antimony is oxidized. The furnace products are antimony-rich (5 to 9%) slag and low antimony (less than 1%) lead. 

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. 

Lead—antimony or lead—arsenic ahoys must not be mixed with lead—calcium (aluminum) ahoys in the molten state. Addition of lead—calcium—aluminum ahoys to lead—antimony ahoys results in reaction of calcium or aluminum with the antimony and arsenic to form arsenides and antimonides. The dross containing the arsenides and antimonides floats to the surface of the molten lead ahoy and may generate poisonous arsine or stibine if it becomes wet. Care must be taken to prevent mixing of calcium and antimony ahoys and to ensure proper handling of drosses. 

Selenium acts as a grain refiner in lead antimony alloys (114,115). The addition of 0.02% Se to a 2.5% antimonial lead alloy yields a sound casting having a fine-grain stmcture. Battery grids produced from this alloy permit the manufacture of low maintenance and maintenance-free lead—acid batteries with an insignificant loss of electrolyte and good performance stability. 

Tin exists in two ahotropic forms white tin (P) and gray tin (a). White tin, the form which is most familiar, crystallizes in the body-centered tetragonal system. Gray tin has a diamond cubic stmcture and may be formed when very high purity tin is exposed to temperatures well below zero. The ahotropic transformation is retarded if the tin contains smah amounts of bismuth, antimony, or lead. The spontaneous appearance of gray tin is a rare occurrence because the initiation of transformation requires, in some cases, years of exposure at —40° C. Inoculation with a-tin particles accelerates the transformation. 

Catalytic Oxidation. Catalytic oxidation is used only for gaseous streams because combustion reactions take place on the surface of the catalyst which otherwise would be covered by soHd material. Common catalysts are palladium [7440-05-3] and platinum [7440-06-4]. Because of the catalytic boost, operating temperatures and residence times are much lower which reduce operating costs. Catalysts in any treatment system are susceptible to poisoning (masking of or interference with the active sites). Catalysts can be poisoned or deactivated by sulfur, bismuth [7440-69-9] phosphoms [7723-14-0] arsenic, antimony, mercury, lead, zinc, tin [7440-31-5] or halogens (notably chlorine) platinum catalysts can tolerate sulfur compounds, but can be poisoned by chlorine. 

Industrial Consumption. The total consumption of primary antimony fell during the period from 1970 to 1986 (Table 3) because of the declining demand for antimony in most types of metallic uses. Since 1986, the demand for primary antimony in antimonial lead has increased, probably because of an increase in demand for starting—lighting—ignition (SLI) batteries. Total consumption in nonmetallic uses has remained stable. However, an increasing proportion of this is made up of flame retardant uses. Currendy, batteries and flame retardants are the two largest markets for antimony. 

Antimony Alloys. Approximately one-half of the total antimony demand is for metal used in antimony alloys. Antimonial lead is a term used to describe lead alloys containing antimony in proportions of up to 25%. Most commercial lead—antimony alloys have antimony contents less than 11%. The compositions of several important antimony alloys are given in Table 4. 

Of the elements commonly found in lead alloys, zinc and bismuth aggravate corrosion in most circumstances, while additions of copper, tellurium, antimony, nickel, silver, tin, arsenic and calcium may reduce corrosion resistance only slightly, or even improve it depending on the service conditions. Alloying elements that are of increasing importance are calcium especially in maintenance-free battery alloys and selenium, or sulphur combined with copper as nucleants in low antimony battery alloys. Other elements of interest are indium in anodesaluminium in batteries and selenium in chemical lead as a grain refiner ". 

DETERMINATION OF ANTIMONY. COPPER. LEAD AND TIN IN OEARING METAL 12.10... 

Calculate the percentages of antimony, copper, lead, and tin in the alloy. 

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