Wilkens regards the blue colouring principle of ultramarine as a compound of hyposulphite and sulphide of sodium. He considers the presence of iron is not necessary for the production of the blue; whilst Dr. Elsner, in a paper published in 1841, states that about 1 per cent. of iron (which he presumes to be in the state of sulphide) is essential. Rowland Williams asks whether it is not conceivable that the blue colour of ultramarine may be due to the presence of a small quantity of black sulphide of iron, most intimately combined with a colourless or comparatively colourless compound (such as white ultramarine), the whole mass (owing to the dilution of the black sulphide) showing a blue reflection.
Ultramarine is insoluble without decomposition in any known menstruum. According to P. Ebell (Ber. 16), ultramarine, when in the most finely divided state, will remain suspended in pure water for months. The liquid may be filtered unchanged through several layers of Swedish filter paper, and appears perfectly clear when examined in a ¾ in. layer, and on evaporation deposits the ultramarine as a lustrous coating on the sides of the vessel. Rowland Williams repeated the above experiment, and can confirm Ebell’s statement. This result shows the necessity of due precautions being taken during the washing of the ultramarine in the process of manufacture, otherwise a considerable amount of the finely divided blue may be lost. Ultramarine is largely used in calico printing for pigment styles, being fixed on the fibre by means of albumen. It is also employed for blueing linen and cotton, wax candles, lump sugar, &c. Ultramarine is not adulterated to a large extent, the chief sophistication being barium sulphate (barytes), and occasionally chalk and china clay.—(Rowland Williams, in Industries.)
Another writer in Industries says that the manufacture of ultramarine has perhaps hardly received the attention it deserves in England. The importance of the industry has been recognised in Germany, however, and though the palmy days of the trade, when the whole production was in the hands of a few firms, and the price was a matter of private friendly arrangement, are gone for ever, yet the business is in a flourishing state, and should prove lucrative if properly managed. It is a characteristically English failing to overlook branches of business not dealing with large quantities of staple commodities, and thus many of the smaller but remunerative industries have passed out of our hands. When one observes that almost every sheet of ordinary blue official paper is decolorised when accidentally brought into contact with an acid, betraying the fact at once that its colouring matter is ultramarine, one realises that a very considerable consumption for this and similar purposes must take place. Like most trades based upon chemical principles, the manufacture of ultramarine has recently made rapid strides, and some of the latest developments are recorded in a paper by J. Wunder, appearing in a recent number of the Chemiker Zeitung, which is worthy of some attention.
With most people not directly interested in it, the term ultramarine is taken to mean the blue pigment known under that name, the words being reckoned almost synonymous. Others, more erudite, recognise the existence of a green variety, but that the production of such colours as red and violet is possible is scarcely suspected. Of course the blue is the most important, but even that does not correspond to one specific substance, products of different shade being prepared by modifying the process of manufacture. As usually made, ultramarine is formed by heating together carbonate of soda, kaolin, sulphur, and charcoal, with limited access of air, the resulting pigment being green; this, on roasting with sulphur, becomes blue. If the operation be conducted with complete exclusion of air, so-called ultramarine white (in reality grey) is produced, which becomes green on further heating. Ultramarine blue capable of resisting the action of alum is sometimes required, and may be obtained by the use of a highly silicious charge and much sulphur, the burning being conducted in crucibles or in mass according to the purpose for which the pigment is required. The former process is costly, while the latter gives a product containing a good deal of free sulphur, which is objectionable for such purposes as calico printing. Removal of the excess of sulphur by heat or caustic soda is not feasible, as the colour suffers in either case, but a certain amount of success has attended experiments with sodium sulphide, the colour often brightening noticeably.
It is curious that chemically pure sodium carbonate, or such as is made by the ammonia-soda process, is not well fitted for the manufacture of ultramarine; Leblanc soda, containing a little caustic, is distinctly preferable. Sprinkling the soda with a strong solution of sodium sulphide before use is a good plan, and one easy to adopt. The more silicious the mixture the more difficulties are encountered, but the product is a deeper, richer colour, and withstands the action of alum and weak acids better. Excess of oxygen must be guarded against; many a manufacturer has had a batch turn out a hard cold blue, instead of a soft rich colour, solely on account of a too-excellent draught, an accident especially liable to happen in winter time. So much dreaded is this catastrophe that some makers habitually limit the air supply—smothering the neighbourhood with smoke, and wasting coal. The need for exact control here indicated points to a probable advantage from the use of gaseous fuel. Considerable economy has resulted from the use of the waste gases from one furnace serving for the preliminary heating of another; a better plan would probably be the introduction of regenerative heating.
The crude ultramarine as it comes from the furnace contains a large proportion of soluble salts, notably 20 to 24 per cent. of sodium sulphate, which have to be removed before it is merchantable. Usually, after grinding, it is simply stirred up repeatedly with hot water and the aqueous extract is siphoned off. That such a crude method should be in vogue at the present time is very significant of the ample margin of profit that must exist. By systematic extraction and filtration under pressure the washing may be effected with so little water that the solution is sufficiently concentrated to pay for evaporation by the heat of waste furnace gases, the recovered sodium sulphate serving to replace part of the raw material.
The quality of ultramarine largely depending upon its fineness, it is graded by levigation, the coarser portions being filter pressed, and the finest “floating” quality, which remains in suspension for an inconveniently long time, precipitated by the addition of a trace of an ammonium salt, gypsum, or even hard water, and filtered by the aid of a suction tube on the principle of an ordinary Bunsen pump.
The first successful attempt to produce ultramarine violet was made by Professor Leykauf in 1859. By heating ordinary ultramarine with calcium chloride in the presence of air and moisture, he obtained a violet-toned pigment, but it was not a full colour. The active substance in this change was probably hydrochloric acid, produced by the decomposition of the calcium chloride. Later experiments with other reagents, such as chlorine and gaseous hydrochloric acid, led to the following methods being devised. In the first, ultramarine blue is spread out on stoneware shelves in iron chambers and treated with a mixture of chlorine and steam at a temperature of 300° F. to 480° F. for about three hours. In the second, the plant is very similar, but at the bottom of the chambers are stoneware dishes, into which hydrochloric acid is poured from time to time. As the temperature is raised, copious vapours arise from these, evaporation being aided by a strong draught, and the ultramarine blue, after being kept at 428°-446° F. for some seven hours, becomes converted into a dull violet, which brightens on continuing the process with a temperature gradually falling to 320° F. The ultramarine violet produced by either of the above methods resists the action of lime, and is of general applicability.
The pigment produced by a third and simpler process, consisting merely in heating ultramarine blue mixed with salammoniac and a little sodium nitrate, is unfortunately not so stable. Another shade of considerable interest is a pure bright light blue, formed by heating the violet variety in hydrogen to about 536°-554° F. It has not yet been prepared on a commercial scale, but certainly merits the attention of manufacturers. An ultramarine red has been made by acting on the violet produced by either of the first two methods with the vapour of either nitric or hydrochloric acid at 275°-293° F., the sole essential determining condition being the temperature. Iron vessels could be used in the case of nitric acid at this temperature, but if hydrochloric acid were employed stoneware would have to be substituted. In the manufacture of the violet the temperature is above the limit at which hydrochloric acid acts on iron.
It is now only necessary for some successful experimenter to put on the market yellow and orange shades of ultramarine for almost the whole of the spectrum to be represented. The problem of the cause of the colour of ultramarine, attempts to solve which have been repeatedly made, seems increasingly difficult when its protean character is considered; but this from the industrial point of view is of secondary importance, provided all required shades can be produced with ease and economy. Nevertheless, it is certain that here, as in other cases, substantial technical progress would follow from adequate scientific investigation.—(Industries.)