In modern thermometry instruments of extreme accuracy are required, and researches have been made, especially in Germany and France, to ascertain the causes of variability in mercurial thermometers, and how such variability is to be removed or reduced. In all mercurial thermometers there is a slight depression of the ice-point after exposure to high temperatures; it is also not uncommon to find that the readings of two thermometers between the ice- and boiling-points fail to agree at any intermediate temperature, although the ice- and boiling-points of both have been determined together with perfect accuracy, and the intervening spaces have been equally divided. It has been proved that these variations depend to a great extent on the chemical nature of the glass of which the thermometer is made. Special glasses have therefore been produced by Tonnelot in France and at the Jena glass-works in Germany expressly for the manufacture of thermometers for accurate physical measurements; the analyses of these are shown in Table III.
Table III.
| SiO2. | Na2O. | K2O. | CaO. | Al2O3. | MgO. | B2O3. | ZnO. | Depression of Ice-point. | |
| Tonnelot’s “Verre dur” | 70.96 | 12.02 | 0.56 | 14.40 | 1.44 | 0.40 | .. | .. | 0.07 |
| Jena glass— | |||||||||
| XVI.-111 | 67.5 | 14.0 | .. | 7.0 | 2.5 | .. | 2.0 | 7.0 | 0.05 |
| 59-111 | 72.0 | 11.0 | .. | 5.0 | 5.0 | .. | 12.0 | .. | 0.02 |
Since the discovery of the Röntgen rays, experiments have been made to ascertain the effects of the different constituents of glass on the transparency of glass to X-rays. The oxides of lead, barium, zinc and antimony are found perceptibly to retard the rays. The glass tubes, therefore, from which the X-ray bulbs are to be fashioned, must not contain any of these oxides, whereas the glass used for making the funnel-shaped shields, which direct the rays upon the patient and at the same time protect the hands of the operator from the action of the rays, must contain a large proportion of lead.
Among the many developments of the Jena Works, not the least important are the glasses made in the form of a tube, from which gas-chimneys, gauge-glasses and chemical apparatus are fashioned, specially adapted to resist sudden changes of temperature. One method is to form the tube of two layers of glass, one being considerably more expansible than the other.
(C) Sheet and Crown-glass.—Sheet-glass is almost wholly a soda-lime-silicate glass, containing only small quantities of iron, alumina and other impurities. The raw materials used in this manufacture are chosen with considerable care, since the requirements as to the colour of the product are somewhat stringent. The materials ordinarily employed are the following: sand, of good quality, uniform in grain and free from any notable quantity of iron oxide; carbonate of lime, generally in the form of a pure variety of powdered limestone; and sulphate of soda. A certain proportion of soda ash (carbonate of soda) is also used in some works in sheet-glass mixtures, while “decolorizers” (substances intended to remove or reduce the colour of the glass) are also sometimes added, those most generally used being manganese dioxide and arsenic. Another essential ingredient of all glass mixtures containing sulphate of soda is some form of carbon, which is added either as coke, charcoal or anthracite coal; the carbon so introduced aids the reducing substances contained in the atmosphere of the furnace in bringing about the reduction of the sulphate of soda to a condition in which it combines more readily with the silicic acid of the sand. The proportions in which these ingredients are mixed vary according to the exact quality of glass required and with the form and temperature of the melting furnace employed. A good quality of sheet-glass should show, on analysis, a composition approximating to the following: silica (SiO2), 72%; lime (CaO), 13%; soda (Na2O), 14%; and iron and alumina (Fe2O3, Al2O3), 1%. The actual composition, however, of a mixture that will give a glass of this composition cannot be directly calculated from these figures and the known composition of the raw materials, owing to the fact that considerable losses, particularly of alkali, occur during melting.
The fusion of sheet-glass is now generally carried out in gas-fired regenerative tank furnaces. The glass in process of fusion is contained in a basin or tank built up of large blocks of fire-clay and is heated by one or more powerful gas flames which enter the upper part of the furnace chamber through suitable apertures or “ports.” In Europe the gas burnt in these furnaces is derived from special gas-producers, while in some parts of America natural gas is utilized. With producer gas it is necessary to pre-heat both the gas and the air which is supplied for its combustion by passing both through heated regenerators (for an account of the principles of the regenerative furnace see article [Furnace]). In many respects the glass-melting tank resembles the open-hearth steel furnace, but there are certain interesting differences. Thus the dimensions of the largest glass tanks greatly exceed those of the largest steel furnaces; glass furnaces containing up to 250 tons of molten glass have been successfully operated, and owing to the relatively low density of glass this involves very large dimensions. The temperature required in the fusion of sheet-glass and of other glasses produced in tank furnaces is much lower than that attained in steel furnaces, and it is consequently possible to work glass-tanks continuously for many months together; on the other hand, glass is not readily freed from foreign bodies that may become admixed with it, so that the absence of detachable particles is much more essential in glass than in steel melting. Finally, fluid steel can be run or poured off, since it is perfectly fluid, while glass cannot be thus treated, but is withdrawn from the furnace by means of either a ladle or a gatherer’s pipe, and the temperature required for this purpose is much lower than that at which the glass is melted. In a sheet-glass tank there is therefore a gradient of temperature and a continuous passage of material from the hotter end of the furnace where the raw materials are introduced to the cooler end where the glass, free from bubbles and raw material, is withdrawn by the gatherers. For the purpose of the removal of the glass, the cooler end of the furnace is provided with a number of suitable openings, provided with movable covers or shades. The “gatherer” approaches one of these openings, removes the shade and introduces his previously heated “pipe.” This instrument is an iron tube, some 5 ft. long, provided at one end with an enlarged butt and at the other with a wooden covering acting as handle and mouthpiece. The gatherer dips the butt of the pipe into the molten “metal” and withdraws upon it a small ball of viscous glass, which he allows to cool in the air while constantly rotating it so as to keep the mass as nearly spherical in shape as he can. When the first ball or “gathering” has cooled sufficiently, the whole is again dipped into the molten glass and a further layer adheres to the pipe-end, thus forming a larger ball. This process is repeated, with slight modifications, until the gathering is of the proper size and weight to yield the sheet which is to be blown. When this is the case the gathering is carried to a block or half-open mould in which it is rolled and blown until it acquires, roughly, the shape of a hemisphere, the flat side being towards the pipe and the convexity away from it; the diameter of this hemisphere is so regulated as to be approximately that of the cylinder which is next to be formed of the viscous mass. From the hemispherical shape the mass of glass is now gradually blown into the form of a short cylinder, and then the pipe with the adherent mass of glass is handed over to the blower proper. This workman stands upon a platform in front of special furnaces which, from their shape and purpose, are called “blowing holes.” The blower repeatedly heats the lower part of the mass of glass and keeps it distended by blowing while he swings it over a deep trench which is provided next to his working platform. In this way the glass is extended into the form of a long cylinder closed at the lower end. The size of cylinder which can be produced in this way depends chiefly upon the dimensions of the working platform and the weight which a man is able to handle freely. The lower end of the cylinder is opened, in the case of small and thin cylinders, by the blower holding his thumb over the mouthpiece of the pipe and simultaneously warming the end of the cylinder in the furnace, the expansion of the imprisoned air and the softening of the glass causing the end of the cylinder to burst open. The blower then heats the end of the cylinder again and rapidly spins the pipe about its axis; the centrifugal effect is sufficient to spread the soft glass at the end to a radius equal to that of the rest of the cylinder. In the case of large and thick cylinders, however, another process of opening the ends is generally employed: an assistant attaches a small lump of hot glass to the domed end, and the heat of this added glass softens the cylinder sufficiently to enable the assistant to cut the end open with a pair of shears; subsequently the open end is spun out to the diameter of the whole as described above. The finished cylinder is next carried to a rack and the pipe detached from it by applying a cold iron to the neck of thick hot glass which connects pipe-butt and cylinder, the neck cracking at the touch. Next, the rest of the connecting neck is detached from the cylinder by the application of a heated iron to the chilled glass. This leaves a cylinder with roughly parallel ends; these ends are cut by the use of a diamond applied internally and then the cylinder is split longitudinally by the same means. The split cylinder is passed to the flattening furnace, where it is exposed to a red heat, sufficient to soften the glass; when soft the cylinder is laid upon a smooth flat slab and flattened down upon it by the careful application of pressure with some form of rubbing implement, which frequently takes the form of a block of charred wood. When flattened, the sheet is moved away from the working opening of the furnace, and pushed to a system of movable grids, by means of which it is slowly moved along a tunnel, away from a source of heat nearly equal in temperature to that of the flattening chamber. The glass thus cools gradually as it passes down the tunnel and is thereby adequately annealed.
The process of sheet-glass manufacture described above is typical of that in use in a large number of works, but many modifications are to be found, particularly in the furnaces in which the glass is melted. In some works, the older method of melting the glass in large pots or crucibles is still adhered to, although the old-fashioned coal-fired furnaces have nearly everywhere given place to the use of producer gas and regenerators. For the production of coloured sheet-glass, however, the employment of pot furnaces is still almost universal, probably because the quantities of glass required of any one tint are insufficient to employ even a small tank furnace continuously; the exact control of the colour is also more readily attained with the smaller bulk of glass which has to be dealt with in pots. The general nature of the colouring ingredients employed, and the colour effects produced by them, have already been mentioned. In coloured sheet-glass, two distinct kinds are to be recognized; in one kind the colouring matter is contained in the body of the glass itself, while in the other the coloured sheet consists of ordinary white glass covered upon one side with a thin coating of intensely coloured glass. The latter kind is known as “flashed,” and is universally employed in the case of colouring matters whose effect is so intense that in any usual thickness of glass they would cause almost entire opacity. Flashed glass is produced by taking either the first or the last gathering in the production of a cylinder out of a crucible containing the coloured “metal,” the other gatherings being taken out of ordinary white sheet-glass. It is important that the thermal expansion of the two materials which are thus incorporated should be nearly alike, as otherwise warping of the finished sheet is liable to result.
Mechanical Processes for the Production of Sheet-glass.—The complicated and indirect process of sheet-glass manufacture has led to numerous inventions aiming at a direct method of production by more or less mechanical means. All the earlier attempts in this direction failed on account of the difficulty of bringing the glass to the machines without introducing air-bells, which are always formed in molten glass when it is ladled or poured from one vessel into another. More modern inventors have therefore adopted the plan of drawing the glass direct from the furnace. In an American process the glass is drawn direct from the molten mass in the tank in a cylindrical form by means of an iron ring previously immersed in the glass, and is kept in shape by means of special devices for cooling it rapidly as it leaves the molten bath. In this process, however, the entire operations of splitting and flattening are retained, and although the mechanical process is said to be in successful commercial operation, it has not as yet made itself felt as a formidable rival to hand-made sheet-glass. An effort at a more direct mechanical process is embodied in the inventions of Foucault which are at present being developed in Germany and Belgium; in this process the glass is drawn from the molten bath in the shape of flat sheets, by the aid of a bar of iron, previously immersed in the glass, the glass receiving its form by being drawn through slots in large fire-bricks, and being kept in shape by rapid chilling produced by the action of air-blasts. The mechanical operation is quite successful for thick sheets, but it is not as yet available for the thinner sheets required for the ordinary purposes of sheet-glass, since with these excessive breakage occurs, while the sheets generally show grooves or lines derived from small irregularities of the drawing orifice. For the production of thick sheets which are subsequently to be polished the process may thus claim considerable success, but it is not as yet possible to produce satisfactory sheet-glass by such means.