Thénard, a French chemist, proposed to make white lead in this way, but it was found that although the colour was pure and good, yet the lead had not sufficient body to satisfy the wishes of artists and painters. White lead has been made for years past according to what is called the Dutch method. Lead is cast into plates, and these plates, in some factories, are rolled into coils. These coils then are immersed in earthen pots; the pots are placed in a row, and a small quantity of vinegar is put into each pot. On the top of one row of pots a board is placed, and then other pots above, and so a stack is made. Between the interstices of the pots is put spent tan, or some other substance which by oxidation will evolve heat, and also carbonic acid gas. Now the heat which is evolved in oxidation of the spent tan is useful in volatilising the acid from the vinegar, and in the presence of this acetate the oxygen of the air oxidises the lead. The oxide of lead is dissolved by the acid, and the normal acetate of lead is formed. More oxide is produced, and this is dissolved by the normal acetate, and then you have basic acetate.

When substances containing carbon are oxidised, carbonic acid is the product of the oxidation when the oxygen is in excess, as in this particular case. Carbonic acid is then formed by the oxidation of the spent tan. The carbonic acid then unites with the oxide of lead which was dissolved in the normal acetate, and a thin film of lead carbonate is formed. These thin films go on forming in succession, until at last nearly the whole of the lead is converted into carbonate, which retains the shape of the original lead. In some cases, gratings of lead are used. When the lead is converted into carbonate, it is ground in water and reduced to a fine powder, and is then made up into the sort of pigments required, either with water or with oil. This is, or rather was, an operation attended with considerable danger to the workmen, who were subjected to what is termed lead-poisoning, to which, unfortunately, many painters, from want of cleanly habits, are subject now.

Dutch Process.—In the words of Mr. Carter Bell, who has read a most interesting paper on the subject before the Society of Chemical Industry, the manufacture of white lead is a most ancient proceeding, and has been pursued with but little variation in the mode of manufacture for some hundreds of years. The Dutch seem to have been the originators of this method of making white lead, which is now so largely conducted in this and other countries.

In this process metallic lead is piled in stacks, and submitted to the action of acetic acid, watery vapour, air, and carbonic acid for some time, by which means the metallic lead becomes gradually converted into white lead.

This method is called the “stack” or Dutch process.

The construction of a stack is a very simple and rude operation. Layers of dung or tan, or a mixture of the two, are so arranged as to imbed a large number of earthenware pots, each containing some acetic acid. These pots are about 4 or 5 inches in diameter, and about 7 or 8 inches high; a coil of lead is placed in each pot, and buckles or gratings of lead supported on oaken bearers are laid across and on top of the pots; boards are laid to cover the whole, and form a floor.

The stack is composed of a number of such layers of pots, bearers, and buckles or gratings, raised one upon another.

A stack chamber is a brick enclosure 10 or 12 feet square, and 20 or 25 feet high; such a chamber will contain about 70 tons of lead when stacked and piled. In a white lead factory several of these chambers are built side by side, and when they are in full operation a set of chambers will contain as much as 700 or 1000 tons of lead.

Only the purest kind of lead will be suitable for conversion in this stack process of making white lead, the common varieties being inadmissible. Messrs. Pontifex and Wood have furnished the following analyses of lead used for white lead making.

The presence of silver, copper and iron in the lead would damage the colour of the white lead resulting, and other admixtures retard or prevent the progress of conversion.

In olden times horse dung was the only imbedding material used in the stack arrangement. This material when heated evolves gases which seriously interfere with the colour of the resulting corrosion. Dung has been almost superseded in this country by tanners’ refuse; in Belgium dung is yet employed, and in some places a mixture of dung and tan.

Where dung is used, the process of corrosion of the lead goes on more quickly than when tan alone is employed, but the use of tan offers great advantages, especially this one: that it does not give off gases that damage the white lead.

The operations of charging and discharging these chambers are principally the work of women, and are most laborious and fatiguing.

In emptying the chambers and stripping the stacks, the women are fully exposed to the heated gases which are yielded by the decomposing tan, and the heated and corroded lead. These gases, in themselves most injurious to health, are not to be compared in this respect to the dust which pervades the air and fills the chamber in which these women work.

When a stack is charged, the chamber containing it is enclosed. The tan or dung within soon commences heating, and the heat soon causes the acetic acid in the pots, and the water in the tan or dung, to rise in vapour and penetrate the stack. Air is admitted to the stack through openings left for that purpose, and carbonic acid is evolved from the heated decomposing tan or dung, and this gas also penetrates the stack, and the process of converting blue lead into the white lead gradually proceeds, and the blue metal becomes corroded and incrusted with a white crust or covering.

As to the exact chemical changes and combinations proceeding in the working of a stack, differences of opinion exist, but we may fairly conclude that the process resolves itself into this—first, the formation of sub-acetate of lead, which, decomposed by the agency of the carbonic acid gas, becomes reduced to the condition of normal acetate by loss of a portion of its basic oxide of lead. The reduced sub-acetate then again takes up an additional molecule of oxide of lead, and is re-converted into its original subsalt state, to be again attacked and reduced by the carbonic acid gas, and so on continually during the working of the stack. It will be evident that the “nascent” state of the various substances disengaged during the chemical changes which are proceeding in the stack is an important factor in this process, and must be taken into account in considering the philosophy of the operation.

It will also be evident that the mode of proceeding in white lead making by the stack process is most crude and clumsy, and a most uncertain method, one governed by rule of thumb, and, by no element of certainty or science. White lead makers, as a rule, know nothing of the chemistry of their subject. This absence of chemical knowledge of the subject, by those who are engaged in this manufacture, may explain the curious circumstance that for hundreds of years this industry has been pursued in the same old-fashioned and uncertain way, and the stack, or Dutch process, still holds its ground and displays little or no advance in knowledge or improvements in its method of proceeding, even in the present age of precision in almost every branch of manufacture. The uncertainty of the stack process is shown most clearly in this: That stacks may work and some do not work. In the latter case all the time and labour spent in forming the stacks, and all the acid they contained, is lost.

No amount of foresight will avail to determine beforehand which stack shall accomplish the conversion of its contained metallic lead, and which will not.

The stacks are generally allowed to remain in operation, after they are charged, three or four months; in this time it is presumed all profitable action in the stack has ceased. The temperature of the stack, which had risen gradually from the normal temperature to 100° or 150° F., will have gradually fallen, and this falling temperature is the indication that the corrosion of the lead in the stack has terminated.

After the three months’ action of the stacks, they are stripped and pulled to pieces. Some will be found to be done better than others, and one part of the same stack will be done more perfectly than another. The coating on the lead will also differ; some will be smooth, regular, and equal in formation, some will be rough and blistered, and far from uniform. The rough blistered casting is rejected as unfit for white lead making: the workmen call it “dross.” The smooth laminated coating is the one preserved for the after manufacture.

It is a curious fact connected with the consideration of the total want of educated guidance in these matters that prevails, that in all factories of this description some chambers are noted as always working well, and others are equally well known to always do their work the reverse of well. No one knows why! No one stays to seek the reason. The factory way goes on filling and emptying these white lead chambers whether the stacks be working well or no.

The incrustation that is most esteemed by the manufacturers of white lead in this old-fashioned style is a hard, china-like material, formed of thin deposits, layer upon layer, in a slow, continuous, regular way. It is at once conceivable that in the rough-and-ready manner of stack manufacture most irregular action must proceed.

It would be almost impossible for the contents of the pile or stack to be submitted to the same action of the gases throughout. Some parts of the stack and its contents will be under more favourable conditions than others, hence the reason why, in practice, it is invariably found that some stacks, and some parts of a stack, work better than others. Under the microscope, this good crust of white lead, the proper incrustation from which to prepare white lead, will be readily seen to consist of very thin coatings or layers of white lead, which have been slowly formed on the metallic lead and piled one upon another to the thickness of an eighth or a quarter of an inch. This formation constitutes the hard, china-like substance, which alone possesses the chemical constitution and the properties to form good white lead paint.

White lead makers, recognising this peculiar incrustation as the only one capable of fulfilling their desired purpose of making good white lead paint, do not even recognise any other as of any service for that purpose, be it good or bad. Such a material, if obtained, however good, would be outside their experience and beyond their philosophy. After the stacks have been stripped, the gratings or buckles with their adhering coating of white lead are moistened with water and are passed through crushing rollers to separate the unconverted lead; then the crust which has been detached is ground under heavy edge runners with water.

This detached crust of white lead will vary much in colour: it will be white in some parts, yellowish or greyish in others. These discolorations arise from various causes, but they are principally caused by the contact of the moist wood and tan. The white lead is now a rough crushed material, very hard, and requiring to be ground to the finest powder. It contains, also, small fragments of blue lead which have passed the crushing rolls, and a quantity of acetate of lead. The presence of acetate of lead is always found in larger or smaller quantities, which vary with every operation, and which invariably accompany white lead produced in the stack.

To remove discolorations—to separate the fragments of metal and to dissolve out the acetate salt—much water and washing are employed. The material is ground with water under the heavy edge runner stones, it then proceeds to a series of horizontal mills, each succeeding mill set closer than its fellow, and is further and further ground to fineness with water. From these mills it runs as a milky liquid to a series of settling tanks, where it is allowed to subside, and the clear fluid is run off to waste, or into tanks to be used over again. This waste water will now contain the colouring matter removed from the incrustation, and the principal portion of the acetate of lead which the incrustation previously contained, and any other soluble matters removed from the washed and ground material. The small fragments of lead which passed the crushing roll and edge runner mills will have been previously removed by subsidence in water.

The white lead deposited in the tanks is in some factories ladled out into skips and agitated by a “dolly,” which further enables the heavy powder to get free from the water in which it is entangled. The moist powder is next placed on trays or dishes, and is conveyed to the stove or drying chamber. Women always perform this work.

The drying or stoving room is a large enclosed space heated by a “cockle” arrangement; rough scaffoldings are erected within this chamber, on which women mount to stow the trays on shelves fitted for the purpose. The trays and their contents remain in the heated atmosphere of this chamber for two or three weeks, by which time they become dry and ready for removal, to be packed in lumps for certain markets, or ground to dry powder and packed in barrels for others.

Women are employed to fill and also to empty the drying or stoving chamber, and during this work they are fully exposed to its contaminating atmosphere. Hot and dry, and charged with fine dusty particles of white lead, it becomes a dangerous trap, and contaminates the blood of those engaged with its deadly poison. It is in this part of the manufacture that the principal damage to health occurs. This is the most laborious work; heat makes it very fatiguing, the atmosphere within this chamber being always much above the exterior air.

Recent Government regulations have sought to curtail these and other evils in this manufacture. Women engaged in these stoves are ordered to wear overclothing, headdress and respirators. The general experience of their practice, notwithstanding Government regulations, is this; that they cannot work in them with ease and convenience, and more often wear the respirator around their necks than in front of nose and mouth. The excessive mortality in women who work in these stacks and stoving houses scarcely requires assertion. Few, even of those who employ them, know the extent of the deadly operation. Recently, medical men have made public that cases are within their knowledge of children born already contaminated with lead poison. Woman labour should surely be restricted by Government enactments in all such deadly occupations.

We may sum up the whole matter as regards white lead making by the stack or Dutch method in a few brief words: It is a most tedious and uncertain operation; it is a most dangerous occupation for all concerned; it is founded upon no true principles of any kind; and of science its whole course is ignorant. White lead making is ruled by a “happy-go-lucky” philosophy. The representatives of this manufacture are completely ignorant of the scientific details relating to it, and hence we may not be surprised to find amongst them an enormous amount of ignorance and prejudice.

Good white lead will not differ materially in its composition by whatever process it may be made, but it may differ seriously in its physical character, and in its fitness to produce a substance adapted to the uses to which white lead paint is applied. Good white lead is a compound which contains hydrate and carbonate of the metal, in the proportions either of one molecule of hydrate of lead combined with two of carbonate, or is made up of one molecule of hydrate with three of carbonate of lead.

If we consider the first compound roughly

PbH₂O₂,2Pb CO₃

white lead will be made up of one part of hydrate and two parts of carbonate of lead.

The second compound roughly estimated

Pb H₂O₂,3Pb CO₃

will be one part of hydrate, combined with three parts of carbonate or lead. The latter will be in the proportion of 75 per cent, of carbonate and 25 per cent, of hydrate of lead, and this represents the composition which has been assigned to good white lead by those most acquainted with the subject. The amount of hydrate contained in white lead should never exceed the proportion above named of 25 per cent., nor should its amount be much below the 25 per cent.

The hydrate contained in the substance serves to unite with the oil in the paint; it forms therewith a drying white and elastic varnish which embraces and holds the particles of white carbonate and prevents their subsidence and separation in the paint. There is a chemical action of a much more intimate character between the components of good white lead when mixed with oil which neither of the constituents of this compound can alone produce.

For instance, hydrate of lead and linseed oil produce a varnish-like substance, semi-transparent and of no covering capability.

Carbonate of lead and linseed oil produce a compound which is opaque, but has no body or covering power, and in which the white solid carbonate is held in feeble mechanical suspension.

Neither of them constitutes a paint, but when together as white lead they are mixed with oil, combination takes place, and serviceable paint of good body and covering power and enduring quality is produced. Good white lead is a dense, perfectly amorphous powder of perfect whiteness, possessed of great body and covering power when combined with oil. When mixed with linseed oil and used as paint it rapidly dries in the air and assumes a varnish-like, glossy, hard surface, and is capable when once dry of resisting the action of air and water for any length of time. It does not weep when laid on a surface with a brush, that is, the oil does not separate from the solid material of the paint.

Attempts have been made to produce white lead quickly and cheaply by precipitating processes, but in all such methods the resulting compound is deficient in certain special qualities absolutely necessary to white lead proper and to its uses. The precipitated white lead is always of a crystalline structure, and crystalline lead can never furnish a good body paint—no amount of pulverising and grinding of this crystalline material will correct this defect in its nature, and deprive it of its crystalline form.

“Once a crystal always a crystal” has an especial application to this point of our philosophy. Pulverising a crystal will not alter its structure, but simply reduces the size of the crystals. Crystals of white lead are unable to effect the necessary combination with the oil and form the true varnish which white amorphous lead so readily produces. Paint made with the precipitated white lead lacks body and covering power, and this because of the absence of this chemical union with the oil.

The manufacture of white lead by process of precipitation, even were the resulting preparation suitable, does not correct the evils of the present method by Dutch or stack process of making white lead.

A solution of lead may be precipitated in a few minutes, but it cannot be made so quickly. The white lead, after its precipitation, has to be filtered or separated, washed and dried, and ground to powder, which processes cannot occupy less time than a few weeks for completion.

Precipitated white lead has been made in France and Germany for some years, and it is now manufactured in those countries. It is now made in England by one patent process, but the product lacks certain qualities, and is consequently still open to the objections already noted.

Substitutes for white lead of a non-poisonous nature, or of such a nature as not to produce such deadly effects in their preparation or use as white lead does, have been proposed; their introduction has not, however, been a great success. A mixture of sulphate, sulphide and oxide of zinc is a patent white made by subliming galena in an oxidising furnace or hearth. This compound lacks body.

All of these so-called substitutes are very inferior to white lead, not only as to quality but as to cost. They cannot compete with white lead. A committee of enquiry on these substitutes for white lead, reporting the result of their enquiry and examination, stated that they found that these were mostly prepared with varnishes before they were sold for use, and that in most instances they were mixed with a large quantity of driers, and that the drier invariably was a compound of lead.

The principal consumption of white lead is for paint; to produce this paint it is ground with oil in varying proportions, about 8 to 15 per cent. This produces the ordinary white lead in oil, and is worth from 19l. to 20l. a ton, but often more than this amount.

Dry powdered white lead is chiefly made for and used by grinders and mixers, who combine with it a variety of other cheaper materials—chalk, clay, sulphate of lime, and sulphate of baryta, but principal use is made of chalk and barytes. These are mixed with the white lead, and then the mixture is ground with oil and formed into paint, sold under various names according to quality: thus—guaranteed white lead, firsts, seconds, thirds, and fourths, the proportion of white lead diminishing, and that of the adulterant increasing, as we descend from the pure material. Guaranteed and best white lead is not pure, and does not mean pure white lead. Pure white lead can be purchased at some makers, but its price, if pure, can never fall below 19l. or 20l. per ton.

To sophisticate white lead, and produce the various inferiors named, dry powdered white lead is needed as a starting point, and for this purpose principally arises the necessity for its production. If ground in oil the adulterants cannot be properly incorporated with it. Dry white lead is used for nothing else that could ever give rise to any great demand for it. We have already observed that the production of this dry and powdered white lead is the most dangerous proceeding connected with this industry. Grinding in oil is unattended with any important consequence to the health and comfort of those employed. A serious drawback to the “stack” production, the china-like incrustation to which reference has already been made, is that it requires crushing, grinding, washing, and drying, and a second course of dry grinding after it is dried—the most objectionable step in its preparation.

Could the corrosion of the blue lead be effected in such a way as to prevent any discoloration of the material by the tan and wood—could the corrosion be so produced as to be easily separated from the buckle or grating on which it has formed—could this separation be so effected as to prevent the breaking up of the lead skeleton, and the presence of small pieces of metal in the detached crust of white lead, two principal reasons for washing and drying are removed.

There is yet another consideration, that is, the presence of acetate of lead, always found in varying quantities in the incrustation produced, and remaining at the close of the operation and conversion. To remove this, careful washing, and after-stoving and drying must be accomplished. The amount of this salt present is found to differ with each operation, and in various portions of the same make.

The washing out of the acetate is never perfect, and it involves a large amount of labour.

Opinions differ as to the effect of this acetate if allowed to remain in the product. White lead makers on the “stack” principle aver that it should and must be washed out, lest it should damage the qualities of the paint. This is questionable, and not one can produce practical evidence of its being the cause of any damage if still contained in white lead. Facts seem to deny its harmfulness in this respect, inasmuch as the best prepared samples, those washed and dried from the most careful makers, will be found upon analysis to contain more or less of acetate of lead.

A large proportion of this salt in white lead may not be beneficial for many reasons, but a small percentage can do no harm; nay, for many purposes it may be good.

There is no substance used for driers for white lead that is more esteemed than this acetate of lead, commonly known as “sugar of lead.”

A small amount of this salt present in white lead would communicate drying properties, and this alone is what it could do.

Granting that we can discover a method of producing white lead of amorphous character, of good density, free from all discoloration, free from all particles of metallic lead, and free from all but a small percentage of acetate of lead, then washing will not be needed.

Stoving and drying become unnecessary. The work of women, their deadly occupation, so burdensome to the operatives and to all with whom they are concerned, is done away with.

Condy’s Process.—An improvement in the manufacture of white lead was patented by Condy, of Battersea, in 1881, which, though giving perfectly satisfactory results when carefully conducted, necessitated special precautions, and led to his substituting in practice the following additions and modifications, which are of great consequence in rendering the process more certain in the quality of its product, and more valuable as a commercial manufacture on the practical scale, by virtue of its offering greatly increased facility and economy in production.

The results of numerous and repeated experiments on the larger scale induced Condy to qualify the recommendation contained in his first patent, viz. that of employing a solution of tribasic acetate of lead and bicarbonate of soda in proper proportion to precipitate nearly the whole of the lead, and further stating that he preferred to employ “a slight excess of tribasic lead salt rather than find carbonate of soda in excess.” Though, when carefully conducted, if the greatest nicety is observed, a satisfactory result is obtained; in practice, the least variation from the exact composition of the two substances is attended with the drawback that the white lead is liable to a slight uncertainty of tint after it is ground in oil, whereas by the process hereinafter described a positive and reliable result can be obtained, as the white lead produced will be of a uniform white colour, and not liable to turn when ground in oil. Though the earlier process was in itself complete for the manufacture of white lead from oxide of lead, it afterwards occurred to Condy that a great object would be attained in rendering the process more valuable and more practical, if a method were devised, worked out, and described for the manufacture of tribasic acetate of lead to be made entirely from metallic lead by the action of acetic acid or neutral acetate of lead on metallic lead, and not to be dependent on the employment in any way of previously manufactured oxide of lead.

This portion of Condy’s invention relating to the manufacture of tribasic acetate of lead may be described as follows: he melts, and, after skimming carefully, feathers the metallic lead by dropping it into water; he places this granulated lead in wooden vessels or vats previously fitted with perforated false bottoms under which are fixed taps for drawing the liquor off into other vats or tanks placed on a lower level. Having filled with granulated lead the vessels fitted with the false bottoms, he fills up the interstices with a dilute acetic acid composed of one part, by weight, of acid (specific gravity 1·045 at 60° F.) and 12½ parts of water, and after allowing the dilute acid to stand for two hours, draws it off through the taps into the lower tanks. This allows access of atmospheric air to the lead, which has the effect of heating the lead so that oxidation takes place.

After a time (about three or four hours), this oxidation begins to slacken, when he pumps up a second time the acid solution from the lower vat on to the granulated lead, and allows them to stand in contact for one hour; he then again draws off the liquid into the lower tank, and again exposes the metallic lead to atmospheric oxidation, allowing three or four hours for the latter operation; and if the solution of lead has not already attained the specific gravity of 1·040, at 60° F., he again repasses the liquor over the metallic lead partially oxidised, until it has attained that specific gravity, when he places the dissolved lead with fresh granulated lead and recommences the manufacture in the same way.

This operation succeeds much better on the large scale than on a laboratory scale. In vats containing upwards of one ton of lead, the result is all that can be desired, and can be obtained by passing the liquor from twice to three times over the metallic lead partially oxidised. A little practice enables the operator so to control the process that he can obtain the solution of the desired specific gravity with perfect ease.

This plan of manufacturing tribasic acetate of lead possesses the advantage of producing that substance wholly or nearly wholly free from the impurities contained in metallic lead, such as copper and silver, which are not taken up, or soluble, in the presence of metallic lead. In consequence of the circumstance that foreign matter is left almost untouched, it is practicable to make white lead of a fine quality from old lead such as lead piping, roofing, and worn out lead generally, which can thus be utilised to greater advantage than in any other way.

Having obtained this solution of basic acetate of lead of the specific gravity of 1·040 at 60° F., Condy proceeds as follows:—To the solution produced by each 60 lb. of acid and 750 lb. of water previously pumped up into another vat or tank, he adds bicarbonate of soda in the proportion of 30 lb. for each 60 lb. by weight of acid originally employed, and agitates the mixture. This will generally precipitate all the white lead, but it is necessary to test the filtrate to ascertain the exact point when all the lead is thrown down. Sufficient bicarbonate of soda should be added to do this completely, and it would be better to use bicarbonate of soda in excess rather than leave any lead unprecipitated, as by this means greater certainty is obtained in securing on the large and practical scale a white lead capable of standing the effect of light and grinding in oil without changing. The white lead after precipitation can be washed, pressed, and dried in the usual way.

The following variation may be made from the method described of making tribasic acetate of lead, thus:—To each 60 lb. of acid and 750 lb. of water may be added sufficient of the tribasic solution to make neutral acetate of lead, with which to recommence the manufacture of tribasic acetate of lead by the process described. Vague reference has been made in works on technical chemistry to the possibility of using metallic lead in the manufacture of sugar of lead, but such references have been practically worthless, as they contain no information of a practical nature even for the manufacture of neutral acetate of lead, and no process at all has ever been described for the manufacture of basic acetate of lead from metallic lead acted on by acetic acid or acetate of lead.

Gardner’s Process.—The conditions observed and fulfilled in the arrangements adopted by Prof. E. V. Gardner, are founded upon a study of the nature, properties and behaviour of the substances concerned, under certain methods of treatment.

There are several oxides of lead which may be formed under special conditions.—(1) Pb₂O, and the same oxide combined with water Pb₂H₂O₂; (2) PbO, and the same oxide combined with water PbH₂O₂. In the hydrated form these oxides combine readily with carbonic acid, but they do not combine readily with carbonic acid when dehydrated. The hydrates are most readily formed at about 120°-130° F., and are decomposed after they are formed if heated to 212° F.

These oxides and their hydrates combine with acetic acid to form acetate and sub-acetate of lead, and with nitric acid to form nitrate and sub-nitrate of lead.

Lead, submitted to the action of air, watery vapour, and acetic or nitric acid, or a mixture of these acids, with air or oxygen, with proper precautions, forms sub-acetate or sub-nitrate of lead, and this sub-acetate or sub-nitrate of lead readily absorbs carbonic acid and forms carbonate and sub-carbonate of lead.

Sufficient acetic or nitric acid, or a mixture of these and air or oxygen, and watery vapour, must be constantly supplied to form the subsalts of lead, to carry on the operation of converting blue lead into white lead; but an excess or an insufficiency of these agents will in either case prevent the formation of sub-acetate or sub-nitrate, and consequently of the sub-carbonates.

Thus—too little air, acetic acid and aqueous vapour prevents the formation of the hydrated sub-acetate and consequently sub-carbonate of lead. Too much acetic acid and aqueous vapour, and too little air forms an acetate on the surface of the lead, which, by the excess of water, dissolves and wastes, and washes the lead; it also varnishes the surface of the lead with a coating of acetate, and checks, if it does not completely prevent, the formation of sub-acetate of lead, and consequently the formation of carbonate and sub-carbonate of lead. Similar rules hold good in the case of nitric acid and the formation of nitrate and sub-nitrate.

The process of forming the hydrated sub-acetate or sub-nitrate of lead is most energetic at a temperature of 120°-130° F. In a lower temperature, a much longer time is occupied in carrying out the process of conversion; while at a higher temperature the delicate sub-acetate or sub-nitrate of lead first formed suffers loss of water, until, at 212° F., it is completely dehydrated. At a temperature about 135° F., the power of forming carbonate and sub-carbonates is lessened, and at 212° F. is considerably diminished. The carbonate itself is dehydrated at 212° F., and is decomposed at a higher temperature.

To obtain a white lead of excellent quality for its various uses, it is necessary to produce a substance which possesses sufficient body to cover surfaces to which it may be applied as paint, and it must possess sufficient base to combine with the oil of the paint to form a vehicle or varnish to retain and hold the body on the surface. This is found to be the case with sub-carbonate of lead, or especially with a compound constituted of two or three equivalents of carbonate of lead, with one equivalent of hydrated oxide of that metal.

Lead, to be attacked by chemical agents, should possess a clean surface. If the surface of the lead is chemically clean, so much the better. The surface of the lead should be extended as much as possible, and exposed to the action of the gases and vapours at a certain heat for its conversion into white lead.

If the most favourable conditions are sought, the temperature should be between 120° and 130° F.; and to carry on the chemical action most satisfactorily, the lead during its conversion should present a granular coating—that is, the coating formed by the chemical agents should be granular and not smooth and continuous in character. It should be porous, and not of a continuous varnish-like or vitreous character.

To rapidly carry on the chemical action, the chemical agents should be well diffused and commingled throughout each other, and the blue lead should be so exposed as to be open to their attack on all parts of its surface equally, and all should be at, and kept at, a proper temperature and a proper degree of humidity. Too dry a heat prevents the process of conversion. Too moist an atmosphere wastes the materials and arrests their action. The conditions, therefore, which are most favourable will be a certain humid atmosphere of well diffused and commingled vapours or gases, acting on metallic lead exposed to them under the physical conditions described, and at a temperature between 110° and 135° F.

These favourable conditions can be further augmented by certain electrical arrangements in connection with them.

Again, in the sources from which the carbonic acid is derived, and in the arrangement of the apparatus for applying the carbonic acid, favourable and unfavourable conditions can be imported. Thus, by using paraffin, petroleum, benzine, or light oil of paraffin or petroleum, or similar carbonaceous substances free from sulphur, or mixtures of such carbonaceous substances either alone or mixed with air or other oxidising substance, comparatively pure carbonic acid may be furnished without at the same time producing any objectionable compounds.

As a result of his researches and experiments, Prof. Gardner has proposed (Eng. Pat. 1882, No. 731) certain improvements in the method of converting blue lead into white lead, in the apparatus employed, and in the method of making and applying the carbonic acid used in the process. Some of these improvements are applicable to the open stack or chamber process, while others relate to closed chambers.

Preferably, for the conversion of blue lead into white lead, Prof. Gardner adopts a closed, but not air-tight, chamber. This chamber is ventilated or relieved so as to enable the incoming gases and vapours to enter it without hindrance, and to escape by means of an exit valve and pipe, or an exit shaft, connected with the chamber, communicating with the exterior air, and regulated by a valve or damper. The gases and vapours within the chamber can find their way out by this exit shaft only, by slight pressure on expansion from within the chamber; thus the interior of the chamber is preserved from disturbance, by preventing the formation of currents within its atmosphere, and yet a perfect circulation of the gases and vapours is kept up.

To warm the interior of this chamber, which is constructed of any material that will resist the action of the vapours and gases, and which is not too absorbent, Prof. Gardner makes the bottom of the chamber of such a shape as to form a heating vessel to hold water or steam, this water or steam, or both, being kept at the required temperature by means of a steam coil. Matters are so arranged that the contents of this coil are protected from any excess of pressure, and consequently the temperature seldom or never exceeds about 212° F., unless for any special reason it is desired to raise it to a higher point. Sometimes the sides are constructed similarly to the bottom.

The materials of which these chambers are constructed must be capable of resisting the heated and acidified vapours within them. Cast or wrought iron faced with glass, slate, tiles, pewter, or glazed bricks; tinned copper, tinned brass, or pewter; timber, whether green or after carbonising by heat or sulphuric acid; all are more or less suitable. Means of observing the progress of the conversion, and means of lifting the contents in or out, must also be provided, as well as thermometers to indicate the temperature prevailing inside.

The gases and vapours which effect the conversion of the blue lead into white lead are generated outside the chamber just described, and are conducted into it by means of pipes, being first raised to such a temperature in excess of that which should exist inside the converting chamber as to allow for the cooling effect arising from the friction and loss of heat in passing through the various pipes and distributors attached to the converting chamber.

Owing to this extra heating, the gases and vapours are expanded, diffused, and commingled, and do not rob the interior of the converting chamber of any heat on entering it, so that the heat inside the converting chamber is kept constant, and can operate to further expand and diffuse the gases and vapours in contact with the blue lead inside the chamber. In practice it is found that the temperature of the converting chamber cannot be suitably controlled if any portion of the gases or vapours be generated within that chamber.

The blue lead is arranged in the converting chamber in trays, or on shelves or frames, so as to allow it to be completely surrounded and attacked by the vapours or gases, and thereby be converted into white lead, at the same time preventing the formation of direct currents or eddies. Framed supports resembling a dinner waggon serve well for holding the lead, and may easily be arranged to lift bodily in and out of the chamber with their burden of blue or white lead. The surface on which the blue lead is directly supported is made of graphitic carbon, hard coke, platinum, or carbonised or platinised material, such as is used for plates in electric batteries, or of other material standing in a similar electrical relationship to lead, or capable of generating with it an electric current.

In applying this development of electrical energy to the ordinary “stack,” as for instance the Dutch process, the pots containing the acetous liquid and blue lead are made of, or lined with, such electrical carbon, or contain a portion of it in suspension, by which the same effect is realised. Advantage may also be derived from furnishing a supplementary supply of carbonic acid to the stack beyond that due to the decomposing dung, &c.; as well as from injecting a current of air or oxygen at suitable temperatures, and from the admission of steam in a coil throughout the stack.

The generation or production of the acetic or nitric acid vapours is attained by heat in a vessel so arranged that its contents are kept at a certain temperature for vaporising, by having the boiling acid solution at about 1·003 sp. gr., procured by mixing water with vinegar or acetic or nitric acids.

The supply pipes conveying the air or oxygen and the carbonic acid, or either of them, can easily be made to emit their contents close to the boiling acid solution, whereby the vapours arising from the latter are mixed and intermingled with them, and all pass together through the pipes and distributors into the converting chamber or stack.

In preparing the carbonic acid it is necessary to observe certain precautions, especially that it shall be pure and that no carbonic oxide shall gain admission to the chamber. If the ordinary chalk and carbon method be employed, the furnace must be provided at the uptake with a series of air inlets, so as to ensure that the gases passing from the furnace to the delivery tube shall be most thoroughly oxidised.

The purification of the carbonic acid may be effected in the usual way by passing it through a vessel containing water; or, if requisite, it may be cleansed, expanded, and heated in one operation by passing it through or over hot water, or over a hot aqueous solution of carbonate of soda, all of which, however, incur considerable cost in plant and manipulation.

Owing to these difficulties in purifying carbonic acid, Prof. Gardner prefers to prepare a practically pure carbonic acid in the first place, and this he does by allowing petroleum, benzine, paraffin, or other hydrocarbon or carbonaceous liquid to gradually fall into a retort containing chalk or other suitable carbonate at a high temperature, whereby relatively pure carbonic acid gas is generated; and while still in a highly heated state it encounters a stream of air or oxygen, ensuring its complete combustion before entering the converting chamber.

Another method of procuring fairly pure carbonic acid is by the combustion and oxidation of any of the liquid hydrocarbons mentioned above, in suitable lamps; and when carbonic acid gas of exceptional purity is required, it may be obtained by heating bicarbonates to a sufficient degree to drive off one molecule of carbonic acid, reducing the bicarbonate to carbonate, from which it can be reproduced by treatment with carbonic acid gas obtained from cheaper sources.

The modus operandi adopted by Prof. Gardner is as follows: The lead is granulated and prepared for conversion in one operation, thus—an iron or a slate slab about 2-3 inches thick is placed in a tank containing acetic or nitric acid solutions rising about 3 inches above the upper surface of the slab. The lead is melted at low red heat and poured from a height of 4 to 6 feet into the acid solution, through which it falls till it encounters the slab, and thereupon passes away into the surrounding solution, being thus converted into a spongy condition. In this condition the lead is spread on frames or trays, which are then lifted bodily into their places in the converting chambers. The latter is closed and heated to 120° F. for 3-4 hours, or until the whole contents have assumed a uniform temperature. Thereupon the acid vapours and air are admitted and distributed, taking care that the temperature is not thereby reduced below 110° F. nor increased above 125° F., steam being temporarily shut off if necessary. This treatment is continued for 24 hours.

The admission of aqueous vapour should be so regulated that while a dry atmosphere is avoided, yet there is no appreciable condensation of moisture in the chamber. While ensuring this condition, the temperature may reach as high as 130° F. for a second period of 24 hours, but must not overstep the limits of 120° F. minimum and 135° F. maximum.

After 48 hours’ treatment, the supply of duly warmed carbonic acid gas is admitted for a period of two hours, without discontinuing the introduction of acid vapours, air and steam; and this addition of carbonating gas is repeated for two hours at a time with intervals of four hours during which it is cut off. When, after four or five days, efflorescence or exfoliation appears on the lead, the supply of carbonic gas is increased to two hours in every four, or four in every six; and the admission of acid vapours, air and steam may also be augmented so long as the temperature is not allowed to exceed 130°-135°F. The whole operation is completed in seven to fourteen days.

Of this process, Mr. Carter Bell, in his paper before referred to, speaks in the highest terms. No washing or drying is necessary. No women are engaged in the manufacture, and but few men. The white lead thus produced by the aid of electricity is deposited in a peculiar state of disintegration, it is perfectly amorphous and non-crystalline, of the purest quality; its density is 5·8. When ground in oil and made into paint, it possesses great body and a covering power inferior to no other paint, if not superior to them all.

Painters who have used the paint, practical men, and amongst these we may observe coach painters, have pronounced its excellence and superiority to the best ordinary white lead paint.

By this electrical process of manufacture, not only is the time consumed in the making and in the preparation of this material greatly shortened, but the cost of preparation is reduced, and added to this is the important fact, the vital factor in our consideration. The labour of women is unnecessary. No lives are sacrificed to its working requirements.

Prof. E. V. Gardner, who has been for some years occupying his attention with the subject of white lead making, with a view especially to remedying its existing evils, has invented his electrical chamber process of manufacture, and an entirely new course of after treatment. He has for the last seven or eight years been more or less occupied perfecting his conception, and accommodating it to practical and commercial claims.

Chamber processes are not new, there have been several patents enrolled for making white lead in closed chambers, but none has proved commercially convenient or practically successful in its adaptation, and none has survived to the present time.

In Germany, white lead is made in chambers at the present day. The lead in gratings or sheets is supported on wooden rods, saddle fashion, the chamber is then filled, and its contents are submitted to currents of acetic acid vapour, air, steam, and carbonic acid gas; the time needful for conversion is six or seven weeks. The after steps in the separation of the incrustation, and its preparation for trade purposes are much the same as in the “stack” product preparation. It is washed, stoved, dried, and ground. The white lead made on the German plan does not differ in any material degree, save it be in price, from the best English commodity. We may assume that the washing and drying in Germany consumes a like period of time to that process in English works, viz. two or three weeks. We then see that the German plan of making white lead cannot be perfected in less than eight or ten weeks’ time from the commencement of the corroding action in the chamber. To compare these facts and the efficiency of the different plans described:—

The time required to complete the corrosion in the stack is at least 14 or 16 weeks.

The Gardner’s electric process requires for the same purpose only 14 days.

As to point of time, the German plan excels the stack, and can be carried out in one-half the time required in the stack method of conversion.

The Gardner’s electrical method excels the German, and can be perfected in one-third the time needed for the German chamber operation, and one-sixth the time required the stack.

These figures open out a most important matter when we regard the capital invested and lying dormant in stack lead works.

It is well known that we have in electricity a most powerful agent by which to effect the chemical combination of various substances on the one hand, or on the other, by its means to break up and disrupt a chemical compound. Professor Gardner’s main principle of action in his new process is founded upon these facts, and he takes advantage of electrical power to cause the combination of the lead with the necessary elements to build up white lead in his chambers. He either employs electrical discharges to energise and render active in their chemical affinities the various materials engaged, or he so disposes of them as to form an electric or galvanic combination in the chamber. In the latter arrangement the chamber and its contents represent a gas battery on an extensive scale. In practice he prefers the latter plan; it is more simple, more manageable in the hands of the ordinary workmen. The original plan was to have graphite or graphitic carbon plates or supports for the buckles or gratings of lead within the converting chamber. These carbon plates and the lead to be converted, were so placed as to form a collection of galvanic “couples” or “pairs,” and in this condition were submitted to the gases entering the chamber from without. It will be understood that various modes of arrangement would occur without departing from the principle concerned.

In practice this method answered very well, but presently a difficulty arose; not only were the graphitic carbon or graphitic plates expensive, but they were easily broken, and became friable in use. Carbon plates of an especial kind were manufactured to meet these failures and remedy these defects, not without success, but still open to objection. In looking round for some substitute to replace the carbon, two points were to be kept in view, to seek some electro-negative to lead like the carbon, and some electro-conductive like it, and some material that would bear rough handling such as workmen give, and be practically convenient in its adaptation to a working chamber.

Gold or platinum would excel in these particulars, but there are considerations which debar their use. Pure tin presented itself, and tin was tried with great success. Tin would at first be thought, on account of its close electrical relationship to lead, far from favourable to the purpose. Graphite or carbon would appear far more suitable. Practice pronounced the tin to act as efficiently as carbon. This may at first seem contradictory and strange, but if we consider that while the carbon is certainly more highly electro-negative to lead than tin, yet the tin is the more conductive, and offers the less resistance to the electric current of the two; in this manner the tin compensates by its conductive power all it may lack, as compared with carbon, in electrical energy when coupled up with lead.

Tin plate is now used as the electric-negative element in the chamber of the Gardner plan. Tin plate means pure tin. Ingot tin is rolled out into plates, the bottom of the chamber is covered with this pure tin plate, so are the bearers and the shelves, or supports which are to hold the lead during its conversion. Tin pipes and tin fittings, which resist the action of acetic acid, are also used to conduct the gases to the chamber to carry on the converting operation, and to preserve the product from any source of discoloration.

When a chamber is prepared for the converting operation, the whole of the lead it contains will be in metallic communication with the tin supports, and these with the tin covered bottom of the chamber.

The chamber when working is kept at a certain temperature by a steam coil beneath the floor of the chamber. The process is simple. The lead buckles or gratings are placed on tin-covered stands, somewhat in form and make like a dinner-waggon. The whole is hauled up and dipped into a bath of acetic acid and acetate of lead; it there remains for one or two minutes, it is then hauled out, drained and lifted bodily through the top into the chamber. Other stands filled with buckles are so dipped and so placed till the space of the chamber is fully occupied.

This dipping cleanses the surface of the metal, and when it is exposed to the air it is speedily coated with a hydrated oxide of lead. This is the first step in the process of conversion. The chamber when filled is closed, and its temperature is brought to about 100° F.; then vapour of acetic acid and vapour of water and air are supplied from without to the interior of the chamber. This is continued for 15 or 20 hours. The lead buckles within the chamber will now possess a whitish coating, consisting of subhydrate and subacetate of lead, and they will present a uniform colour. Carbonic acid generated in any convenient manner is next passed into the acid generator; it mixes with the other gases and vapours, and with them goes on its way to supply the chamber. Speedily the action of the carbonic acid is observed, the surface lead becomes quite white and presents the appearance of a snow shower having fallen within the chamber. The formation of white lead is now speedily effected. This treatment is continued throughout the space of 13 days; at the end of this time the supply of acetic acid vapour is stopped, and the supply of air, steam and carbonic acid is continued, according as it is desired to obtain white lead rich in oxide or in carbonate.

After a short further period, steam and air only are sent into the chamber, which is varied in temperature to 120° or 130°F., and lastly the steam supply is stopped; air alone enters the chamber, which is kept heated by the coils beneath the floor. The contents of the chamber are now in a dry state, and the operation is terminated.

It will occur to most readers that these terminal proceedings amount in effect to a convenient method of washing and drying the white lead while it is still attached to the parent lead, and this it is in fact.

The contents of the converting chamber are lifted out through the opened top, and the buckles or gratings with their crust of white lead are turned into the agitator. This agitator is an iron cage revolving inside a closed chamber of the same material. During the revolution of this cylinder or cage, the contained lead gratings fall from side to side, and the incrustation on their surfaces becomes detached and broken up. It falls in, this broken state through the bars of the cage or cylinder into a receptacle beneath. The denuded buckles or gratings are retained in the cylinder and are removed. These gratings or buckles are cast of such a thickness as to withstand two or three converting operations in the chamber before they are recast.

This crude white lead is carried by an elevator, or it falls into the hopper of a pair of granite crushing rolls, also enclosed; and from these it passes into the mixer or incorporator from which it can be removed in a dry state or mixed with oil.

The incrustation of white lead will be found upon examination to be possessed of some peculiarities, the result of the electrical action which has been going on within the chamber. It is quite white. It falls from the lead buckle or grating which it coats, if the grating be struck against a piece of wood with but a slight blow. It is easily friable, and can be rubbed to the finest powder between the thumb and finger, or on the palm of the hand.

Now, we may explain, as we conceive it, the philosophy of its production in this state of disintegration.

We know that a feeble and prolonged current of electricity will in time deposit metals from their solutions in a crystalline condition, and that if we quicken the current of electricity and cause it more energetically to act on the same solution, we can precipitate the metal from that solution in a state of powder.

It is to similar action of electricity as that to which we last refer that we ascribe the formation of the crust on the gratings of lead in the non-adherent and disintegrated condition in which it is produced, and by reason of which it is so easily detached from the lead and broken up to powder. No edge runner grinding, such as is required by the stack process, is in this case necessary.

The crude white lead and crushed material, whether in a dry state, or incorporated with oil, is finished and ground in a granite roller paint mill, from which it issues as dry white lead, or as white lead in oil.

Paint made from this electric white lead has been sent to America, to France, to Belgium, to Germany for trial, and has also been largely tested in this country by painters, engineers, and others unacquainted with its precise nature, and it has been productive of good results.

Of its density, body, and covering power, there can be no doubt, and never once have these qualities been called in question.

The cost of the manufacture of white lead by the stack process is about 3l. to 3l. 10s. per ton. By the German method, the cost is about the same as by the stack. By Gardner’s electric process, the cost of conversion is 10s. a ton. To this 10s. must be added the cost of labour expended in preparation, an item which cannot be well estimated on the present limited scale of manufacture; it could not exceed an additional 15s. a ton. This would bring the cost of manufacture of electric white lead to 25s. a ton.

In this electric process inferior lead can be operated upon with success. Brands of that metal such as white lead makers by the stack method dare not employ, may be successfully converted in an electric chamber, and with fair results as to the quantity and quality of the white lead produced.

By the use of Gardner’s electric process it would appear that we not only preserve health, but save lives; we not only save time, but interest on large capitals, which lie idle for long periods at a time; and we can economise and simplify the whole manufacture and preparation of white lead, divesting it of all its present cumbersome and unhealthy stages. Gardner’s process, we believe, must take a prominent position as one of the most necessary, valuable, and scientific inventions of modern times.

Hannay’s Process.—Mr. J. B. Hannay, whose name is well known in connection with various chemical and engineering inventions and processes, has recently brought out a process for the manufacture of white lead. The old method of producing white lead or carbonate of lead is one involving much time and labour, together with no small risk to the health of the workpeople. By the new process brought out by Mr. Hannay, sulphate of lead is manufactured direct from galena or lead ore, without the necessity of the intermediate process of the reduction of the ore and the extraction of metallic lead. It is said that the sulphate of lead produced by the new process is whiter and more permanent than the carbonate.

The process is described as follows:—A furnace, 36 in. by 30 in., and 48 in. deep, contracting to a narrow chamber about 36 in. long by 14 in. wide, communicating with the main flue, is charged with coke and brought to a red heat. The bed of coke is so thick as to be almost up to the level of the sill of the furnace door. The lead ore is not charged in large quantity and left for an indefinite time, but is thrown in in quantities of a few shovelfuls at a time, the object being to effect extremely rapid volatilisation and consequent oxidation. The proportion of ore to fuel is 1 ton to 1 ton, and the result is said to be the conversion of 95 per cent. of the charge into its equivalent in white lead. In the first or wide chamber, the coke is oxidised, carbonic oxide being the resulting gas, the rapid volatilisation of the galena or sulphide of lead also taking place in the same chamber. On entering the inner portion of the furnace, the volatilised sulphide of lead and the carbonic oxide are converted into carbonic acid and sulphate of lead.

Forced blast has been employed to cause the high temperature necessary for the volatilisation of the ore; but it has been found unnecessary, admission of air at atmospheric pressure through tuyere holes being quite adequate. After leaving the inner chamber of the furnace, the gases pass into a flue, level with the furnace, and about 40 feet long by 16 square feet in sectional area. From this flue the gases pass into a tower about 20 feet high, and from thence into wrought-iron flues 3 feet in diameter. These flues terminate in a wrought-iron chest, in which are fitted two steam injectors. The gases are forced by these injectors into the central chambers of the condensers. These condensers are two in number, and contain a central chamber, 16 feet by 12 inches, into which the gases are forced as described. The gases escape through interstices into the outer chambers of the condenser, and are there condensed, a continuous stream of water occupying the lower part of the condenser. The waste gases escape by a downcast leading to a tall chimney. The temperature of the gases as they enter the condenser is about 840° F.

The product is pumped from the condensers to a settling vat. Here it settles for an hour, the deposit being pumped into a second vat and washed with dilute sulphuric acid, in order to remove impurities. The resulting product is washed several times with water, and is then passed through a filter press. From the press it drops into bogies, which carry the pulp to the drying house, where it is dried by hot air. The process would thus appear an extremely simple and practical one. Several chemical authorities of repute, as well as manufacturing firms and others who have used the new white lead, have expressed themselves strongly as to its merits. One point immensely in favour of sulphate of lead as opposed to carbonate, is that the former is almost entirely innocuous, whereas the poisonous properties of the other are well known. It is claimed that the sulphate is not acted upon by coal gas or by the atmosphere of towns, which is always more or less impregnated with gases such as sulphuretted hydrogen, whose reactions with various metals have only too good reason to be known.

According to the patent specification bearing the names of French and Hannay, they employ lead ores, lead fume, or lead slags containing sulphur; and when these materials do not contain sufficient sulphur to form a sulphate with all the lead which sublimes in the process, they add to them pyrites or other sulphur-yielding substance to make up the deficiency. They heat the materials mixed with a suitable proportion of coke in an air-blast cupola furnace, which is by preference of an improved and special construction shown in Figs. 18 to 20, and hereinafter described; and they thereby produce sulphite of lead as a sublimate, provided that there are no chlorides such as common salt present in the charge, in which case sulphate and chloride of lead will be formed.

The sublimate is carried forward with the current of gases through flues to a fume condenser, which is by preference of the kind known as Wilson’s and French’s. As the gases and sublimate pass through the flues, hydrochloric acid is mixed