All the black pigments in use owe their colour to carbon, and all are produced by artificial means, no natural form of carbon possessing the requisite qualities. Several manufactured carbonaceous substances are known in commerce under the generic name of “Blacks.” The most important of these are animal-black, bone-black, Frankfort-black, ivory-black, and lamp-black. They are usually obtained by carbonising organic matter, particularly bones, in closed vessels or crucibles, or by collecting the soot formed by the combustion of oily, resinous, and bituminous substances. Other blacks than those enumerated are manufactured, but only on so small a scale as to be of no commercial importance. Carbon, lamp, and vegetable blacks consist almost entirely of carbon, containing usually from 98 to 99½ per cent. of that substance, the residue consisting of a little ash, water, and occasionally unburnt oil. Bone and ivory blacks, on the other hand, are chiefly composed of mineral matter, which may amount to 65 or 75 per cent. and is mainly represented by phosphate of lime. Their actual colouring matter, the carbon, only constitutes 15 to 30 per cent. of the mass. The balance is water and unburnt animal tissue. Blacks prepared from animal matters other than bone and ivory carry 40 to 80 per cent. of carbon, and their mineral matter is generally in the form of carbonates of lime and of the alkalies. The principal impurity to be watchful of in the vegetable and lamp blacks is a small quantity of oily matter which Animal-black.—This substance is almost identical with bone-black, but is generally in a more finely divided state. Any animal refuse matter may be used in its preparation, such as albumen, gelatine, horn shavings, &c. These are subjected to dry distillation in an earthenware retort. An inflammable gas is given off, together with much oily matter, ammonia, and water, while a black carbonaceous mass is left behind. This is washed with water and powdered in a mill, the product being animal-black. It is largely used in the manufacture of paint, printing ink, and blacking. Bone-black.—When bones are heated in a retort or crucible, the organic constituents are decomposed and carbonised. A mixture of combustible gases is given off; some of these do not condense on cooling, others condense in the form of a heavy oil, called bone-oil. Also much water containing tarry water and ammoniacal salts in solution passes The process, as worked on the large scale, is carried on in different ways, according as it is desired to collect the volatile condensable portion of the distillate, or to allow it to escape. In the latter case, when it is required to obtain only bone-black, the apparatus employed is of a very simple nature, and the amount of fuel needed is comparatively small. The carbonisation is effected in fire-clay crucibles, 16 in. high and 12 in. diameter. These are to be preferred to crucibles made of iron, which were much used at one time, since they do not lose their round form when subjected to a high temperature; in consequence of this, they fit more closely together in the furnace, less air can penetrate, and therefore less of the charcoal is consumed by oxidation. The furnace is an ordinary flat hearth, having a superficial area of about 40 square yards, and is covered in with a flat arch, all of brickwork. The fireplace is situate in the middle of the hearth; the crucibles are introduced through doors in the front, which are bricked up when the furnace is filled; each furnace holds eighteen crucibles. The crucibles, filled with the coarsely broken bones, are covered with a lid luted on with clay. To economise fuel, the furnaces should be in a row, and placed back to back. The arrangement of the furnace and pots is shown in Figs. 1 and 2. A is the fireplace; B, the crucibles, eighteen in number, spread over the floor of the furnace in a single layer; c, d, e, and f are the flues for conducting away the heated gases arising from the calcination of the bones, as well as the waste heat itself; the last portion of the flue is fitted with a damper g. The furnaces are intended to be built in fours, back to back, the waste heat serving in a great measure to Figs. 1 and 2.—Bone-black Furnace. When the furnace is filled and the doors are bricked up, the heat is slowly raised to redness, at which point it is kept for six or eight hours. The combustible gases are evolved and consumed in the furnace as the bones begin to decompose, and by this means so much heat is produced that only a A furnace such as that described above will carbonise four charges of bones in one day, each charge being more than half a ton in weight. With careful work, the bones will yield 60 per cent. of bone-black, or more than one ton daily. If it be required to condense the volatile gaseous products of the carbonisation, this process is conducted in retorts similar to those used in the manufacture of acetic acid from wood: these are so arranged that the whole of the gaseous products are condensed and collected. The aqueous portion of the distillate is usually evaporated down to obtain salts of Ordinary bone-black has about the following composition: Phosphate and carbonate of lime, and sulphide or oxide of iron, 88 parts; charcoal, containing a small quantity of nitrogenous matter, 10 parts; silicated carbide of iron, 2 parts. The decolorising properties of bone-black are due solely to the presence of the charcoal. When intended for use as a deodoriser or decoloriser, bone-black should be kept carefully excluded from the air, for by exposure it loses this power to a great extent, and becomes almost inert. That which has been freshly burned is therefore best for these purposes. The cost of production of bone-black may be calculated as follows:—
Bone-black never has the depth or brilliancy of lamp-black, but it mixes well with either water or oil, and though a slow drier as an oil paint, is permanent and not high priced. Frankfort-black or Drop-black.—This is a black powder obtained from dried vine-twigs carbonised to a full black and then ground very fine. On a large scale it is prepared from a mixture of vine-twigs, wine-lees, peach-stones, bone-shavings, and ivory refuse. It varies in shade according as the animal or vegetable charcoal is in excess; when the latter predominates, the powder is of a bluish colour; but when there is an excess of animal charcoal, it has a brownish tinge. It is customary to wash the powder well when first made, in order to remove any soluble inorganic impurities. The finest Frankfort-black is probably the soot obtained from the combustion of the materials mentioned above. It makes an excellent pigment, and is extensively used by copperplate engravers in the preparation of their ink. Drop-black is simply Frankfort-black ground exceedingly fine, mixed with a little glue water, and dried in pear-shaped drops for sale. Ivory-black.—Ivory-black is a beautiful black pigment prepared by carbonising waste fragments and turnings of ivory. These are exposed to a red heat for some hours in crucibles, great care being taken to avoid overheating or burning. When quite cold, the crucibles are opened, and the contents are pulverised, the richest coloured fragments being kept apart for the best quality. The powder is then levigated on a porphyry slab, washed well with hot water on a filter, and dried in an oven at a temperature not exceeding 212° F. The product is of a very beautiful velvety black colour, superior even to that obtained from peach-kernels, and quite free from the reddish tinge which so often characterises bone-black. Ivory-black, like Frankfort-black, is employed by copperplate printers in the preparation of their ink. Mixed with white lead, it affords a rich pearl-grey pigment. Lamp-black.—Lamp-black is an exceedingly light, dull-black powder, formed by the imperfect combustion of oils, fats, resins, &c. It may be prepared on a small scale by [Image unavailable.] Figs. 3 and 4.—Apparatus for making Lamp-black. An especially fine quality of lamp-black is obtained from bone-oil, deprived of the ammonia with which it is always contaminated. It is manufactured on a commercial scale by means of the apparatus shown in Figs. 3 and 4. The oil is [Image unavailable.] Fig. 5.—Apparatus for making Lamp-black. The old-fashioned method of preparing lamp-black from the incomplete combustion of gas tar is conducted in an apparatus resembling that shown in Fig. 5. The furnace a, lined with fire-brick, contains a kettle b, and is surmounted by a large thick cast-iron hood c, communicating with a stone or brick condensing chamber, divided by means of perforated partition walls into three unequal sized compartments d, e, f, wherein the black is deposited. A chimney g delivers uncondensed vapours into the atmosphere. In working, the furnace is first brought to a red heat, then the kettle b, charged with tar, is introduced. As a charge is finished, more tar is added, with occasional stirring, till the kettle becomes inconveniently full of residue, when it is withdrawn and a fresh one replaces it. The residue is chipped out and used as fuel. The black is removed weekly through the door h. It is of good quality and colour so long as the combustion is conducted with a minimum of air, admission of which is controlled at the furnace. The yield is about 25 per cent. of the weight of the tar; and one furnace should treat a ton of tar in a week. One workman can manage several furnaces. An improved process has been introduced by Martin and Grafton for the preparation of lamp-black from coal-tar, which affords a very good product. The coal-tar is first stirred up energetically with lime-water in any convenient vessel, after which the mixture is allowed to stand until the coal-tar has subsided to the bottom, when the lime-water is drawn off. The tar is then well washed by decantation with hot water, and rectified in the ordinary naphtha still. Afterwards it is run into a long iron cylinder, which is placed over a furnace, and supplied with numerous large burners. Each burner has a metal funnel placed immediately above it, connected with a cast-iron pipe, into which all the fumes from each burner are conducted. The naphtha in the cylinder is heated almost to the boiling point by the furnace beneath. A series of smaller pipes lead away the fumes from the main pipe into a row of chambers, and thence into a series of large canvas bags, placed side by side, and connected alternately at top and bottom. The bags vary in number from fifty to eighty, the last one being left open to allow the smoke to escape, after traversing some 400 yards since leaving the burners. The best quality of lamp-black is found in the last bags, that near the furnace being much coarser and less pure. The bags are emptied whenever they contain a sufficient quantity. The process employed in Germany for the manufacture of lamp-black is to conduct the products of the combustion of any resinous matter in a furnace into a long flue, at the end of which is placed a loose hood, made of some woollen material, and suspended by a rope and pulley. The lamp-black collects in this hood, and, when a sufficient quantity has accumulated, is shaken down and removed. In this manner about 6 cwt. of lamp-black may be collected in twenty-four hours. One form of the apparatus is shown in Fig. 6. The circular structure a is lined inside with hanging cloths upon which the black can condense, and is covered with a [Image unavailable.] Fig. 6.—Apparatus for making Lamp-black. In England, an inferior variety is sometimes obtained from the flues of coke-ovens. That known as Russian lamp-black is made by burning chips of resinous deal or pine wood, and collecting the soot formed; but it is objectionable, owing to its liability to take fire spontaneously when left for a long time moistened with oil. A modified form of apparatus has been introduced by Thalwitzer, a German manufacturer, and is shown in Figs. 7 and 8. A vertical tube is provided at its upper end with a funnel, into which cooling water is poured and flows out through openings in the tube immediately above a circular plate of thin cast or wrought iron arranged horizontally and [Image unavailable.] Figs. 7 and 8.—Thalwitzer’s Lamp-black Apparatus. secured at its centre to the tube. Round the periphery of this plate is a vertical rim of tin plate, at the top of which is a pipe through which the cooling water runs into a gutter round the top of the cylindrical casing, the water being The operation is as follows:—The vertical tube is caused to revolve by the action of the worm-wheel, the circular plate thereby receiving a slow rotary movement; and a small stream of water being poured into the funnel at the top of the tube, this water passes down the latter and through the openings on to the circular plate, which is thus kept cool. The burning lamp filled with paraffin or other oil is brought as near to the circular plate as is necessary for the cooling of the flame and the most perfect extraction of the carbon, which, in the form of soot, attaches itself readily to the plate, owing to its coldness and to the condensation of the steam produced. The revolving plate presents continually to the flames a new and clean surface, in consequence of the lamp-black being scraped away by the scraper as soon as deposited, and brought away through a pipe or shoot into a collecting barrel. The apparatus as shown in Figs. 7 and 8 consists of a round metal plate A, provided with a flange a, and fixed on a vertical shaft b supported by the bearing B, and carrying at its upper end a worm wheel d set in motion by a worm. The plate A is cooled by water admitted through a pipe g, and the flange a is provided with a discharge pipe h, through which the cooling water runs into the groove D, surrounding the whole apparatus. Underneath the plate A a number of lamps J are applied, which are fed with oil by a common pipe l. H is an oblique scratcher or blade, the working edge of which is formed by a strip of leather, and touches the lower surface of the plate A. For manufacturing lamp-black, a slow rotary motion is imparted to the apparatus by means of the worm and worm-wheel, and a slight current of water is directed upon the plate A through the pipe g. The lamps J, filled with paraffin oil derived from lignite, or with any other suitable oil, are ignited and approached to the plate A as far as is necessary for cooling the flame, so as to deposit the greatest possible quantity of black. The latter adheres to the cold surface of the plate, which is also kept damp by the aqueous vapour formed during the combustion. The revolution of the plate serves to bring the flame continually into contact with new and clean portions of the plate, the black being continually scraped off by the blade or scraper placed opposite the flames, and conducted through a channel into a collecting trough. There is a risk of overburning, causing a grey tint and a hard and granular texture. A variety of lamp-black known as “carbon black” or “gas black,” has of late years assumed an important position among black pigments. It is produced in considerable quantities in the United States by the combustion of the natural gas issuing from the earth in the mineral oil regions. The soot arising from the imperfect combustion of the gaseous hydrocarbon is made to deposit itself on cooled iron surfaces. These at first were made stationary, but now take the form of revolving discs or cylinders, which are automatically cleansed of the black as fast as it is deposited. This type of lamp-black is remarkably free from mineral impurities and unburned oil, and of a full colour. An improved lamp-black kiln has been introduced in which the use of water is dispensed with. It is shown in Figs. 9 and 10. The furnace A, which is preferably built double, as shown, is constructed of brick lined with firebrick, with a rear wall a that divides the furnace room from the condensing room, side walls b, front c, and central dividing wall d, that divides the furnace into two long and narrow fire [Image unavailable.] Figs. 9 and 10.—American Lamp-black Kiln. spaces. The bottom of the fire spaces e is formed by a sheet iron plate f that is supported by the walls, and the space below plate f serves as an air space through which air circulates by openings g in the front and side walls, this A very large proportion of the lamp-black now made is derived from the combustion of creosote or anthracene oils from coal tar, or of the residues of shale-oil distillation. The form of combustion chamber varies in different works, but is typified by the following rough sketch of that in use at the Stampshaw Chemical Works (Fig. 11). [Image unavailable.] Fig. 11.—Apparatus for making Lamp-black from Creosote or Shale Oil. At these works a horizontal brick flue a about 18 inches square and about 10 feet long is provided. At one end it enters the black-house b, and is here provided with a damper c to shut it off when not working. The other end opens to the air, and here is a sliding door d which, when shut down, leaves an opening round a small pipe e, which enters in this situation from a main pipe that conveys oil in a similar manner to four burners of this description placed side by side. At the bottom of the flue is an iron tray f to catch any liquid that falls from the tube, and in this tray the oil is burned. The burning of oil in one of these flues is not allowed to go on for more than three hours, and, when the combustion is over, the communication with the black-house is closed, the entrance door of the flue is opened, and the cover is taken off the chimney g so that the flue may become cooled, and another flue is taken into use. The black-house is a brick chamber into which the smoke passes, and where it deposits its sooty particles. In some works there is only one undivided chamber; in other works there are more than one, and the chambers communicate by flues through which the smoke passes from one to another. At other works the chamber is divided by vertical In some works, the black from the black-house is also calcined, the object of the “calcination” being to get rid of all greasiness, a point of great importance when the lamp-black is to be used for making fine pigment. This process is conducted in circular iron pans, usually about 2¼ feet high and 2¼ feet diameter, which are provided with removable iron covers. A pan of this size will hold about 2 lb. of lamp-black. A bowlful is first put in and lighted by a red-hot iron; more and more is added from time to time as the ignition proceeds. When the pan, being full, leaves off smoking, the calcination is known to be complete, and the pan is then covered and its contents are allowed to cool. The loss undergone in this process is about 25 per cent. The smoke which comes off is acrid and very irritating to the eyes, like that proceeding from boiling oil, and it is difficult for a person unaccustomed to it to remain many minutes in the chamber where calcining is going on. This process is sometimes conducted within a chamber, but frequently under a shed or even in a building freely open to the air. There are three sources from which nuisance may arise in lamp-black making: 1. The smoke which issues from the chimney of the black-house, small as it sometimes is, often constitutes a nuisance to near neighbours; but the nuisance is not a very serious one, and it does not extend very far from the works, never to a greater distance than about 50 yards. The odour, even when but little smoke escapes, is oppressive and suffocating in character, and resembles that The best mode of preventing nuisance from the black-house is so to elongate the chamber as to give abundant opportunity for the soot to deposit in the course of the smoke along it to the outlet, and by taking means to consume by fire what little smoke escapes deposition. A most effectual arrangement for the accomplishment of these ends is to have a black-house 150 feet long, and so divided by partitions within as to cause the smoke to traverse a distance of altogether 500 feet before it finds an exit; the exit from the chamber communicating with a fire, in which the last of the smoke is consumed, and which serves to assist in regulating the draught through the chamber. The regulation of the draught through the burner and black chamber is of importance in order to avoid the escape of smoke from the burners. If the draught be too great, too much black is lost from the chamber, but if, on the other hand, it be too little, the smoke instead of passing into the chamber will come out into the works and create a nuisance, especially where the burners are erected in the open air, under circumstances in which variation in the force of the wind cannot fail to interfere with due regulation of draught. This part of the manufacture should be conducted within a building of some sort. The best mode of preventing nuisance from calcination is in operation at Shackell & Edwards’ works, in Hornsey Road, Islington. At these works the black is calcined in a chamber The transport of lamp-black is effected in barrels or bags; when in the latter, these should be previously soaked in water containing some clay in suspension, which stops up the pores of the sacking, and thereby prevents loss. The particular virtue of lamp-black as a pigment lies in its state of extremely fine division, which could not possibly be attained by artificial means; this quality renders it invaluable as the basis of black pigments, all of which contain it in a greater or less quantity. Indian ink and printers’ ink are also composed principally of this substance. Unimportant Blacks.—In addition to the recognised blacks already noticed there are a number of other sources of black pigment which have been drawn upon to a limited extent, or have been suggested as substitutes for the standard articles. They only merit a short description. Aniline black is prepared by adding an acidified (sulphuric) solution of bichromate of potash to an aqueous solution of hydrochlorate of aniline, and washing the precipitate. The cost is prohibitive. Candle black is candle smoke condensed on a cold plate. Charcoal black is finely-ground wood charcoal. Coal black has been suggested by grinding coal, but lacks the requisite qualities of a pigment. Cork black is a very fine pigment prepared by calcining cork refuse. Limited supply. German black is Frankfort black. Iron black is ground black sulphide of iron. Lead black is prepared by boiling lead fume in sulphide of soda solution. It would probably be unstable on account of oxidation. Manganese black is ground oxide of manganese. It is costly, and dries too quickly. Prussian black is calcined Prussian blue. It is not of a good colour, nor economical. Prussiate black is the carbonaceous residue from making yellow prussiate of potash. Used chiefly for decolorising syrups, &c. Spanish black is cork black. Tannin black is proposed to be made by exhausting the tannin from refuse leather and tanning agents, and adding alum and sulphate of iron. The colour is blue-black, weak, and unstable. |