Large quantities of lead carrying gold and silver are sold to refiners in bars weighing about 100 lbs. each. The assay of these alloys presents no special difficulties, but the sampling of them is a question which may be profitably discussed.

A molten metal may be conceived to have all the physical states observed in ordinary liquids, although these cannot be actually seen owing to its opaqueness. There is no doubt that pure lead at a temperature only a little above its melting-point can contain a large proportion of gold in such a manner that it may in a figurative way be spoken of as a clear solution. Any small portion withdrawn from the molten metal would afford a perfect sample. The same would be true of any pure alloy of lead and silver in which the silver does not exceed the proportion of 2½ per cent. On the other hand, if the molten metal contains much more than .5 per cent, of zinc, more than .1 per cent, of copper, or a larger quantity of silver, it may be likened to a turbid liquor. The resemblance holds good so far that if the molten lead be further heated, whereby its solvent power on the added metal is increased, the turbidity will disappear, or at least be considerably diminished. A portion taken at random from such a molten metal may, or may not, give a good sample. The suspended insoluble matter will tend to concentrate itself in the upper or lower parts of the liquid according to whether it is heavier or lighter than it; and this separation may occur with extreme slowness or with fair rapidity. However, it is generally agreed that in the case of such alloys as occur in practice, samples taken in this way are quite satisfactory and are the best obtainable. The precautions insisted on are that the lead shall be made as hot as practicable; that it shall be stirred up at the time of taking the sample; and that the portion withdrawn shall be taken out with a ladle at least as hot as the molten metal. The further precaution that if any dross be on the surface of the metal it shall be skimmed off and separately sampled and assayed is almost too obvious to require mention. An alternative and, perhaps, better way of taking the sample is to withdraw portions at equal intervals from the stream of metal whilst the pot is being emptied; equal weights taken from these portions and mixed (by melting or in some other way) give a fair sample of the whole. In addition, separate assays of each portion will show to what extent the metal lacks uniformity in composition. For example, samples taken at the beginning, middle, and end of a run gave the following results in ozs. of silver per ton: 475, 472, 466, showing an average result of 471 ozs. Fifteen fractions taken at regular intervals during the same pouring ranged from 475 ozs. to 464 ozs.: the average result was 469.8 ozs. The same lead cast into bars and sampled by sawing gave an average of 470 ozs. In another case samples drawn at the beginning, middle, and end of a run gave 1345 ozs., 1335 ozs. and 1331 ozs. The mean result in such cases is always a reasonably safe one, but evidently where the metal varies a good deal it is safer to take more than three dips.

Imagine such lead run into moulds and allowed to become solid as bars; the difference between bar and bar would not be greater than that between corresponding dip samples. But in each bar the distribution of the silver and gold is very seriously affected during solidification. Chips taken from the same bar of auriferous lead may show in one place 23 ozs. of gold to the ton, in another 39 ozs.; similarly with silver they may vary as much as from 900 ozs. to 1500 ozs. to the ton.

This rearrangement of the constituents of a bar takes place whilst the lead is partly solid, partly liquid. The most useful conception of such half-solidified metal is that of a felted spongy mass of skeleton crystals of comparatively pure lead saturated with a still fluid enriched alloy. If the solidification of an ingot of impure tin be watched it will be evident that the frosted appearance of the surface is due to the withdrawal of the fluid portion from a mat of crystals of purer tin which have been for some time solid and a contraction of the mass. The shrinking of the last part to become solid is further shown by the collapse of the surface of the ingot where weakest; that is, a furrow is formed on the flat surface. In other cases of fused metal there is expansion instead of contraction in this final stage of the solidification, and the enriched alloy then causes the upper face of the ingot to bulge outwards. There are other causes effecting the redistribution of the metals through the ingot. There can be no general rule of wide application showing which part of a bar is richest and which poorest in the precious metals. This will depend on the quantities of gold or silver, on the quantities and kinds of other metals present and on the manner of casting. The student is advised to consult Mr. Claudet’s paper which has been already referred to.

The best method of sampling such bars is to melt them all down and to take a dip sample of the molten metal in one or other of the methods already described. According to Mr. Claudet this should be done in all cases where the gold exceeds one or two ounces or where the silver exceeds 200 ozs. to the ton. If during the melting down some dross has formed this must be skimmed off, weighed and separately sampled and assayed. The clean lead also must be weighed, sampled and assayed. The mean result must be calculated. Thus 14 tons 5 cwts. of clean lead assaying 32 ozs. to the ton will contain 456 ozs. of silver; 15 cwt. dross assaying 20 ozs. to the ton will contain 15 ozs. of silver. The 15 tons of lead and dross will contain 471 ozs. of silver or 31.4 ozs. per ton.

Of the methods of sampling which avoid melting the bars, that known as sawing is the only one which is thoroughly satisfactory. In it the bars are brought to a circular saw having fine teeth and are sawn across either completely or halfway through; in this way a quantity of lead sawdust is obtained (say 1 lb. or so from a bar) which represents exactly the average of the bar along the particular cross section taken and approximately that of the whole bar. A bar of lead, which by dip assay gave 334 ozs. to the ton, gave on three transverse sections 333 ozs., 335 ozs. and 331 ozs. The variation may be greater than this, but with a large number of bars, where each bar is cut across in as far as possible a different place, these variations tend to neutralise each other and a good sample is obtained. Two or three cwt. of sawdust may be obtained in this way; this is thoroughly mixed and reduced by quartering in the usual way or by a mechanical sampler. A sample of 2 or 3 lbs. is sent to the assayer. This being contaminated with the oil used in lubricating the saw is freed from it by washing with carbon bisulphide, ether or benzene and dried. Then, after mixing, 100 to 200 grams of it are carefully weighed and placed in a hot crucible, the heat of which should be sufficient to melt all the lead. The molten lead should not be overheated and should show no loss due to the melting. The removal of the oil may have decreased the weight by perhaps one half per cent. If the lead gives dross on heating it may be melted under 10 or 20 grams of potassium cyanide, which prevents the formation of dross. Samples are sometimes taken with a drill, gouge or chisel, though no method of this kind is quite satisfactory. One plan adopted is to use a punch which, when driven into the bar, gives a core or rod of metal about half as long as the bar is thick and about one-eighth of an inch across. With five bars side by side it is customary to drive in the punch at one end on the first bar, and at the opposite end on the last one, and on the others in intermediate positions in such a manner that all the holes will be along a diagonal of the rectangle enclosing the bars. The bars are then turned over and similar portions punched out through the bottoms of the bars and along the other diagonal. Or one set of five may be sampled along the top and the next set along the bottom of the bars.

Silver and gold present in bars of copper are subject to the same irregularity of distribution as in lead. The sampling of such bars is guided by the same principles.