Hydrofluoric acid attacks all silicate glasses, liberating silicon fluoride. Use is made of this acid reaction in decorating glasswares in " Etching," by exposing the surface of glass to the fumes of hydrofluoric acid gas in some form.
The most permanent glasses are those containing the highest proportion of silica in solution, but the available heat necessary to decompose such highly silicious mixtures is limited by the present known refractory materials which can be procured for constructing the furnaces. Quartz glassware is a highly silicious glass. It is now made and used in the manufacture of special chemical apparatus and laboratory ware such as crucibles, muffles, etc., which have to withstand severe physical and chemical tests. This quartz glass possesses remarkable features in its low coefficient of expansion and resistance to heat changes. It is highly refractory. Articles made of this glass can be heated to red heat and plunged directly into cold water several times without fracture. Several varieties of quartz glass are now manufactured, and a new field for investigation is presented in applying the features and properties of this glass for use in chemical processes.
In a purely physical sense glass is a supercooled liquid, the silicates are only in mutual solution with each other, and they appear to be constantly changing. Glass cannot be described as a homogeneous or definite chemical compound. Many of the after effects and changes which occur in glass, and the formation of crystals in the devitrification of glass tend to prove the above assertion. The colour changes which take place when ruby and opalescent glass is re-heated, and even the change in colour of glass going through the lehr, cannot be explained unless in the above sense of viewing these remarkable changes. Glasses with an excess of lime in their composition are more subject to devitrification than lead glasses or those of moderate lime content constructed from more complex formulas. The presence of a small proportion of alumina in glass prevents this tendency to devitrification and ensures permanency. Those glasses which have the highest silica content, and which have been produced at the highest temperatures, show the greatest stability in use. Bohemian glasses of this type contain as much as 75 per cent, silica, and are produced in gas-fired regenerative or recuperative furnaces, where the heat approaches 1,500° Centigrade. Such glass is much sought after for enamelling on, being harder and less easily softened by the muffle heat firing on the enamels used. Taking two corresponding glasses of the same basicity, or proportion of silicic acid to the bases present, those formulae which have the greater complexity of bases produce the more fusible glasses. A multiple of bases constituting a more active flux than a single base content, it follows that a compound mixture of silicates fuses or melts at a lower temperature than the respective simple silicates would. These facts are useful in constructing commercial formulae for glasses.
Glasses containing lead oxide as an ingredient are subject to reduction when exposed to flames of a carbonaceous nature. The carbon partially reduces the lead oxide to its metallic state, forming a black deposit. On this account, lead glasses cannot be used in blowpipe working with the ease with which soda-lime glasses can be worked, without reduction taking place. English crystal glass, which contains a high percentage of lead, is usually melted in hooded or covered pots to prevent the carbonaceous flames of the furnace reducing the lead and otherwise destroying the clearness of the glassware. Soda-lime glass and others without the presence of lead can be melted in open pots without any fear of reduction. Modern gas-fired recuperative furnaces, in which more complete combustion of the carbon takes place, can now be used for melting lead glasses in open pots, thus presenting a great saving in the fuel required to melt and produce such glass, besides permitting the use of a cheaper form of pot. This cannot be done with the ordinary English coal-fired furnaces.
Advantage is taken of the reducing action of the coal-gas flame when producing lustre and iridescent glassware. A small proportion of easily reducible metal, such as silver or bismuth, is introduced into the glass and first melted under oxidising conditions. It is then reduced in after-working by flaming, which deposits the metal in a thin sheen upon the surface of the glass, where it comes in contact with the reducing flames. An example of this effect is shown in Tiffany lustre ware, in which silver chloride is used and reduced within the glass, giving a pretty coloured iridescence on the surface, due to the reflection of light from the particles of metal deposited under the surface.
" Aventurine " is a form of glass in which copper and iron oxides are introduced under reducing conditions during melting. The glass is then allowed to cool slowly. The metallic copper tends to separate out in small spangled crystals, which give a pretty sparkling effect. The use of strong reducing agents with very slow annealing is necessary to produce this effect. Copper and gold ruby-coloured glass presents other instances of partial precipitation of the metal by reduction within the glass. According to the extent of reduction, the glass ranges in colour from yellow ruby to brown.
The manganese silicate is readily affected by oxidising or reducing conditions, the purple colour being present under oxidising influences and a greenish-grey colour under reducing conditions. In using manganese as a decolorizer, the glass maker may have added too much of it to his glass, in which case it shows too prominent a purple colour. To destroy this excess of colour he pushes either a little strip of green willow wood or a clean potato to the bottom of the pot of metal. The reducing action of the carbonaceous gas involved takes out the excess of purple colour by partially reducing the manganese present to a colourless state.
The colour of glass is gradually affected in course of time by sunlight. This change in colour is often noticeable in old plate windows, the glass having developed a yellowish green tint in course of time from the action of the solar rays.
Glass which has been incompletely fused or not sufficiently melted to give a complete solution of the materials present is in a weakened state of cohesion and is liable to disintegration. An excess of alkali, lead, or borates used in the glass compositions also tends to early disintegration. A continual exudation and crystallisation of salt takes place upon the surface until the glass wholly disintegrates away to a white powdered salt.
Glass is a poor conductor of heat. When a piece of glass has been expanded under the influence of heat, and is rapidly cooled, the superficial outer portions become intensely strained and contracted upon the interior portions, which retain the heat longer. Under these conditions of cooling, glass is apt to " fly," or collapse and fall to pieces, owing to the outer portions giving way under the great strain. These stresses or strains are relieved in the process of annealing, under which they are gradually eased by a slow and regular cooling from the heated condition. Certain glasses, the composition of which shows considerable differences in the density of the respective bases present, are more subject to this defect than those in which the bases are of more even density and homogeneous in character. Such glasses should be " de-graded " and re-melted in order more thoroughly to diffuse and distribute the denser portions throughout the mass. In de-grading glass, the hot glass is ladled out and quenched in cold water, dried, and re-used as " cullet."