Silica-based

Of the various glass families of commercial interest, most are based on silica, or silicon dioxide (SiO₂), a mineral that is found in great abundance in nature—particularly in quartz and beach sands. Glass made exclusively of silica is known as silica glass, or vitreous silica. (It is also called fused quartz if derived from the melting of quartz crystals.) Silica glass is used where high service temperature, very high thermal shock resistance, high chemical durability, very low electrical conductivity, and good ultraviolet transparency are desired. However, for most glass products, such as containers, windows, and lightbulbs, the primary criteria are low cost and good durability, and the glasses that best meet these criteria are based on the soda-lime-silica system. Examples of these glasses are shown in the table Composition of representative oxide glasses.

After silica, the many “soda-lime” glasses have as their primary constituents soda, or sodium oxide (Na₂O; usually derived from sodium carbonate, or soda ash), and lime, or calcium oxide (CaO; commonly derived from roasted limestone). To this basic formula other ingredients may be added in order to obtain varying properties. For instance, by adding sodium fluoride or calcium fluoride, a translucent but not transparent product known as opal glass can be obtained. Another silica-based variation is borosilicate glass, which is used where high thermal shock resistance and high chemical durability are desired—as in chemical glassware and automobile headlamps. In the past, leaded “crystal” tableware was made of glass containing high amounts of lead oxide (PbO), which imparted to the product a high refractive index (hence the brilliance), a high elastic modulus (hence the sonority, or “ring”), and a long working range of temperatures. Lead oxide is also a major component in glass solders or in sealing glasses with low firing temperatures.

Other silica-based glasses are the aluminosilicate glasses, which are intermediate between vitreous silica and the more common soda-lime-silica glasses in thermal properties as well as cost; glass fibres such as E glass and S glass, used in fibre-reinforced plastics and in thermal-insulation wool; and optical glasses containing a multitude of additional major constituents.

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Nonsilica

Oxide glasses not based on silica are of little commercial importance. They are generally phosphates and borates, which have some use in bioresorbable products such as surgical mesh and time-release capsules.

Heavy-metal fluoride glasses

Of the nonoxide glasses, the heavy-metal fluoride glasses (HMFGs) have potential use in telecommunications fibres, owing to their relatively low optical losses. However, they are also extremely difficult to form and have poor chemical durability. The most studied HMFG is the so-called ZBLAN group, containing fluorides of zirconium, barium, lanthanum, aluminum, and sodium.

Glassy metals

Another nonoxide group is the glassy metals, formed by high-speed quenching of fluid metals. Perhaps the most studied glassy metal is a compound of iron, nickel, phosphorus, and boron that is commercially available as Metglas (trademark). It is used in flexible magnetic shielding and power transformers.

Semiconducting solids

A final class of nonoxide, noncrystalline substances is the chalcogenides, which are formed by melting together the chalcogen elements sulfur, selenium, or tellurium with elements from group V (e.g., arsenic, antimony) and group IV (e.g., germanium) of the periodic table. Owing to their semiconducting properties, chalcogenides have found use in threshold and memory switching devices and in xerography. A related end-member of this group is the elemental amorphous semiconductor solids, such as amorphous silicon (a-Si) and amorphous germanium (a-Ge). These materials are the basis of most photovoltaic applications, such as the solar cells in pocket calculators. Amorphous solids have a liquidlike atomic order but are not considered to be true glasses because they do not exhibit a continuous transformation into the liquid state upon heating.

Cooling from the melt

The formation of glass is best understood by examining Figure 1, in which the volume of a given mass of substance is plotted against its temperature. A liquid starts at a high temperature (indicated by point a). The removal of heat causes the state to move along the line ab, as the liquid simultaneously cools and shrinks in volume. In order for a perceptible degree of crystallization to take place, there must be a finite amount of “supercooling” below the freezing point b (which is also the melting point, T_m, of the corresponding crystal). Crystallization is essentially two processes: nucleation (the adoption of a patterned arrangement by a small number of atoms) and growth (extension of that arrangement to surrounding atoms). These processes must take place in the order described, but, since crystal growth kinetics generally precede nucleation with little overlap during cooling, crystallization in a cooling liquid occurs only over a range of temperatures. In Figure 1 this range is shown by the shaded region, with crystallization reaching its maximum probability in the darkest portion, indicated by point c.

If cooling is conducted rapidly enough, measurable crystallization will not take place; instead, the mass will continue along line abcf, its volume shrinking with falling temperature and its viscosity rising enormously. Eventually, the supercooled liquid will become so viscous that its volume will shrink at a slower rate, and finally it will become a seemingly rigid solid, indicated in Figure 1 by point g. At this point it is called glass.

The glass transformation range

The transformation from the seemingly liquid state (the supercooled liquid) to the seemingly solid state (glass) is gradual, with no evidence of any discontinuities in properties. The transition takes place over a range of temperatures called the glass transformation range; in Figure 1 it is shown by the smooth departure of line abcg from line abcf, which is known as the equilibrium liquid line. (Not shown in Figure 1 is the glass transition temperature, or T_g; this would be located at the lower end of the transformation range.) In crystallization, on the other hand, the transition from liquid to solid takes place with essentially a discontinuous change in volume. In Figure 1 this abrupt transition is indicated by a sharp drop, within the shaded crystallization region, from the liquid line abcf to the crystal line de. With further cooling, the solid follows the crystal line to point e. With few exceptions, the volume of the crystal is less than that of the glass, since the orderly arrangement of atoms in a crystalline solid does not permit as great a free volume as occurs in a glassy solid.

Cooling a supercooled liquid at slower rates causes the material to shrink to a lesser volume, continuing along the line abcf until a glass is formed at point h. Glass at point h is denser than glass at g (with the known exception of vitreous silica). The structure of glass at h is assumed to be identical to that of the liquid at (T_f)₁. Known as the fictive temperature, (T_f)₁ is the temperature at which the liquid structure is frozen into the glassy state. (T_f)₂ represents the fictive temperature of the glass formed by fast cooling.

Reheating

Upon being reheated at all practical rates, glass always remains below its cooling curve, never retracing it. In fact, when reheating is slow enough, the volume actually shrinks in the transition range. In Figure 1 this phenomenon is shown by the dashed line that, after beginning at h, dips below the equilibrium line and eventually meets it at a higher temperature. The volume of a crystal, on the other hand, converts discontinuously, increasing abruptly when the solid is reheated to a liquid at the melting point d.

Sodium silicate glass

1 of 2

2 of 2

The introduction to this article referred to W.H. Zachariasen’s classic definition of glass as a three-dimensional network of atoms forming a solid that lacks periodicity, or ordered pattern. Just such a random atomic arrangement as would appear in a sodium silicate glass is shown schematically in Figure 2. Here the building blocks of the glass network are polyhedra formed around what is known as a network-forming (NWF) cation—that is, a positively charged ion such as, in this case, silicon (Si⁴⁺). The four positive charges of the silicon ion lead it to form bonds with four oxygen atoms, forming SiO₄ tetrahedra, or four-sided pyramidal shapes, connected to each other at the corners. An oxygen atom that connects two tetrahedra is known as a bridging oxygen. An oxygen atom joined to only one silicon atom is a nonbridging oxygen; its one remaining negative charge is satisfied by bonding to a network-modifying (NWM) cation—in this case, a univalent sodium ion (Na⁺)—which occupies an interstice adjacent to the SiO₄ tetrahedron. This corner-sharing tetrahedral structure achieves a liquidlike randomness, rather than a crystalline regularity, because there is a bending of the Si-O-Si bond at the bridging oxygen. In addition, there are twist angles arising between two connecting tetrahedra, as shown in Figure 3.

Nonsilicate glasses

Silica is not the only oxide that fills a network-forming function in glass. Other NWF oxides are the oxides of boron (B³⁺), germanium (Ge⁴⁺), and phosphorus (P⁵⁺). Examples of NWM oxides are those of the alkali ions lithium (Li⁺), sodium (Na⁺), potassium (K⁺), rubidium (Rb⁺), and cesium (Cs⁺) and of the alkaline-earth ions magnesium (Mg²⁺), calcium (Ca²⁺), strontium (Sr²⁺), and barium (Ba²⁺). The oxides of other groups—such as lead oxide (PbO), alumina (aluminum oxide; Al₂O₃), and arsenic oxide (As₂O₅)—often act as intermediates.

Zachariasen’s model

According to Zachariasen, in order for a given oxide A_mO_n to form a glassy solid, it must meet the following criteria: (1) the oxygen should be linked to no more than two atoms of A, (2) the coordination number of the oxygen about A should be small, on the order of 3 or 4, (3) the cation polyhedra must share corners only, and (4) at least three corners must be shared. These criteria are useful guidelines for the forming of conventional oxide glasses, but they reach the limits of their utility in the analysis of nonoxide glasses. Chalcogenide glasses, for instance, are chains of random lengths and random orientation formed by the bonding of the chalcogen elements sulfur, selenium, or tellurium. Ions of these elements have a 2-coordination requirement, and the chains are cross-linked by 3- or 4-coordinated elements such as arsenic, antimony, or germanium.

Kinetic arguments

The most prevalent models for glass formation are based not on structural criteria but on kinetic theories, which are based on the nucleation and crystal-growth factors outlined in the section Volume and temperature changes. After considering these factors, the glassmaker generates a time-temperature-transformation (T-T-T) diagram. In this diagram a curve is plotted showing the heat-treatment times that would be required at various temperatures in order for detectable crystallization to occur. In order for glass formation to take place, the glassmaker would ensure that the cooling rate of the substance exceeded the critical cooling rate for crystal formation—thus bringing into practice the kinetic theory that any substance can be brought to glass if it is cooled rapidly enough.

Density

In the random atomic order of a glassy solid, the atoms are packed less densely than in a corresponding crystal, leaving larger interstitial spaces, or holes between atoms. These interstitial spaces collectively make up what is known as free volume, and they are responsible for the lower density of a glass as opposed to a crystal. For example, the density of silica glass is about 2 percent lower than that of its closest crystalline counterpart, the silica mineral low-cristobalite. The addition of alkali and lime, however, would cause the density of the glass to increase steadily as the network-modifying sodium and calcium ions filled the interstitial spaces. Thus, commercial soda-lime-silica glasses have a density greater than that of low-cristobalite. Density follows additivity behaviour closely.

The densities of representative oxide glasses are shown in the table of properties of oxide glasses.

Elasticity and plasticity

Because of the isotropic nature of glass, only two independent elastic moduli are normally measured: Young’s modulus, which measures the ability of a solid to recover its original dimensions after being subjected to lengthwise tension or compression; and shear modulus, which measures its ability to recover from transverse stress. In oxide glasses, both Young’s modulus and shear modulus do not strongly depend upon the chemical composition.

The hardness of glass is measured by a diamond microindenter. Application of this instrument to a glassy surface leaves clear evidence of plastic deformation—or a permanent change in dimension. Otherwise, plastic deformation of glass (or ductility), which is generally observed in strength tests as the necking of a specimen placed under tension, is not observed; instead, glass failure is brittle—that is, the glass object fractures suddenly and completely. This behaviour can be explained by the atomic structure of a glassy solid. Since the atoms in molten glass are essentially frozen in their amorphous order upon cooling, they do not orient themselves into the sheets or planes that are typical of growing crystalline grains. The absence of such a growth pattern means that no grain boundaries arise between planes of different orientation, and therefore there are no barriers that might prevent defects such as cracks from extending quickly through the material. The absence of dislocations causes glass not to display ductility, the property of yielding and bending like metal.

Strength and fracturing

Glass is exceptionally strong, much stronger than most metals, when tested in the pristine state. Under pure compression, glass may undergo a more or less reversible compression but not fracture. Its theoretical strength in tension is estimated to be 14 to 35 gigapascals (2 to 5 million pounds per square inch); glass fibres produced under very careful drawing conditions have approached 11.5 gigapascals in strength. The strength of most commercial glass products, on the other hand, ranges between only 14 and 175 megapascals (2,000 and 25,000 pounds per square inch), owing to the presence of scratches and microscopic flaws, generally on the surface. Apparently, surface flaws are produced in glass by abrasion with most solids—even by the touch of a finger and particularly by another piece of glass that rubs against it during manufacture. Flaws have a stress-concentrating effect; that is, the effective stress at the tip of a flaw can be easily 100 to 1,000 times greater than that applied. Tensile stresses in excess of a low limit, called the fatigue limit, cause the flaw to undergo a subcritical crack growth. Eventually, depending on the applied stress, the shape of the flaw, the temperature, and even the corrosiveness of the environment, the growth velocity of the crack approaches its terminal limit, and failure becomes imminent. Thus, under a tensile loaded condition, all glass experiences static fatigue and eventually fails. The crack growth velocities are higher with higher magnitudes of tensile stress, sharper flaws (where the tip radius is much smaller than the length), higher temperatures, and higher humidity.

A glass fracture may be examined visually or with a (generally) low-power stereo microscope. Starting from its point of origin, the fracture front travels slowly, producing a nearly semicircular shiny surface called the mirror. The radius of the mirror is inversely related to the fracture stress and, hence, is indicative of the violence of the fracture. (For instance, a thermal fracture generally produces a large mirror, whereas a mechanical fracture often displays a small mirror.) The edges of the mirror have a fine fibrous or misty texture, called the mist. Surrounding the mist are wider and deeper radial ridges, with slivers of glass lifted out. Known as the hackle, these ridges ultimately lead to crack branching. Fracture travels faster in a region that is under tensile stress than in a region of compression; severe compression causes the direction of crack growth to twist, producing a twist hackle or river pattern. Penetration by a pointed object, such as a bullet, often produces what is known as a Hertzian cone fracture, in which an expanding cone of glass is ejected from the side of glass opposite to the impact.

Fractography of glass is important in manufacture and service, in that it is equivalent to a postmortem examination. An experienced fractographer can often pinpoint the origin, the cause, and the circumstances of product failure.

Viscosity

As can be seen from Figure 5, the viscosity of glass, as measured in centimetre-gram-second units known as poise, decreases with rising temperature. Figure 5 also indicates the temperatures at which certain glasses reach standard viscosity reference points that are important in glassmaking. For instance, the working point, the temperature at which a gob of molten glass may be delivered to a forming machine, is equivalent to the temperature at which viscosity is 10⁴ poise. The softening point, at which the glass may slump under its own weight, is defined by a viscosity of 10^7.65 poise, the annealing point by 10¹³ poise, and finally the strain point by 10^14.5 poise. Upon further cooling, viscosity increases rapidly to well beyond 10¹⁸ poise, where it can no longer be measured meaningfully.

The annealing point and the strain point lie in the glass transformation range shown in Figure 1; often, the glass transition temperature (T_g) and the annealing point are used synonymously, and the strain point marks the low-temperature end of the range. The T_g may also be considered the maximum temperature for intermittent service. It is evident from Figure 5 that the T_g of vitreous silica is the highest of the commercial glasses and that increasing the amount of alkali additions (and therefore the concentration of NWM ions) lowers T_g. Of all the various factors affecting viscosity, water, in the form of hydroxyl ions or molecular water, lowers viscosity the most.

Thermal expansion

As is evident from Figure 1, glass normally expands when heated and shrinks when cooled. This thermal expansion of glass is critical to its thermal shock performance (that is, its performance when subjected suddenly to a temperature change). When a hot specimen of glass is suddenly cooled—for example, by plunging it in iced water—great tension may develop in the outside layers owing to their shrinking relative to the inner layers. This tension may lead to cracking. Resistance to such thermal shock is known as the thermal endurance of a glass; it is inversely related to the thermal-expansion coefficient and the thickness of the piece.

Soda-lime-silicates and alkali-lead-silicates, which typically have high expansion coefficients, are quite susceptible to shocking. Improved thermal shock resistance is obtained by using Pyrex-type sodium borosilicates or vitreous silica. For space-based telescopes, the mirror substrates often require materials with expansion coefficients close to zero, in order to avoid any dimensional changes due to temperature fluctuations. A silica glass containing 7.5 percent titanium oxide has a near-zero thermal expansion coefficient and provides satisfactory service in this application.

It should also be evident from Figure 1 that the contraction curve of a glass is significantly different from its expansion curve. When glass is used to seal to other materials such as a metal, the relevant parameter is its effective thermal contraction, not its thermal expansion.

Heat transfer

The thermal conductivity of oxide glass due to atomic vibrations (the so-called phonon mechanism) does not increase appreciably with temperature. On the other hand, the radiation conductivity (thermal conductivity due to photon transport) increases greatly with temperature. Radiation conductivity is also inversely proportional to the absorption coefficient of a glass for specific photon wavelengths. Thus, the rather high radiation conductivity of molten clear glass enables melting to depths of almost two metres, or five feet, in continuous glass tanks without a serious risk of frozen glass at the bottom. Coloured glasses, on the other hand, have a high photon absorption coefficient and therefore need to be melted either to shallow depths or with electric boosting from the bottom of the tank.

Electrical conductivity

Although most glasses contain charged metallic ions capable of carrying an electric current, the high viscosity of glass impedes their movements and electrical activity. Thus, glass is an efficient electrical insulator—though this property varies with viscosity, which in turn is a function of temperature. Indeed, the electrical conductivity of glass increases rapidly with temperature. Hence, in glassmaking it is possible to melt soda-lime-silica glass electrically once it has been heated to about 1,000 °C (1,800 °F) through auxiliary means.

Since univalent alkali ions have the greatest mobility through the glassy structure, they are the primary charge carriers of a glass and therefore determine its electrical conductivity. In general, the higher the concentration of alkalis, the higher the electrical conductivity. The most noted exception from the additivity relationship here is the mixed-alkali effect, in which glasses containing two or more different types of alkali ions have a significantly lower electrical conductivity than linear additivity would suggest. In applications such as high-wattage lamps, where low electrical conductivity is desired, mixed-alkali glasses are useful.

Dielectric constant

The dielectric, or nonconducting, property of glass is important for its use either as a medium separating the plates of a capacitor or as a substrate in integrated circuits. For capacitor usage, the dielectric constant must be high, whereas for substrates it must be low enough to allow high signal speeds between semiconductor chips. In general, the dielectric constant of glass generally increases with the concentration of NWM ions. Therefore, vitreous silica has one of the lowest dielectric constants, while most soda-lime-silicates have high dielectric constants.

Electronic conduction

Electronic conduction of charge is important in only two families of glasses: oxide glasses containing large amounts of transition-metal ions and chalcogenides. In metallic solids there are a large number of weakly bound electrons that can move about freely through the crystal structure, but in insulating solids the electrons are confined to specific energy levels known as valence and conduction bands. As the temperature is raised, some electrons from the valence band are able to jump across to the conduction band, thus contributing to what is known as the intrinsic conductivity of the atom. In extrinsic semiconductivity, on the other hand, electrons are provided by defects in the chemical bonding and by impurity atoms. In oxide glasses containing transition-metal ions, for instance, it is believed that electronic conductivity occurs as the hopping of an electron between two transition-metal ions of differing valence that are separated by an oxygen atom. In chalcogenide glasses, semiconductivity is primarily caused by defective bonds in which a particular atom does not follow its covalent coordination.

Transparency, opacity, and colour

Because electrons in glass molecules are confined to particular energy levels, they cannot absorb and reemit photons (the basic units of light energy) by skipping from one energy band to another and back again. As a consequence, light energy travels through glass instead of being absorbed and reflected, so that glass is transparent. Furthermore, the molecular units in glass are so small in comparison to light waves of ordinary wavelengths that their absorption effect is negligible. Radiation of some wavelengths, however, can cause glass molecules to vibrate, making the glass opaque to those wavelengths. For instance, most oxide glasses are good absorbers of, and are therefore opaque to, ultraviolet radiation of wavelengths smaller than 350 nanometres, or 3,500 angstroms. These glasses can be made more transparent to ultraviolet radiation by increasing the silica content. At the same time, silicate glasses absorb wavelengths greater than 4 micrometres, making them virtually opaque to infrared radiation. Heavy-metal fluoride glasses, on the other hand, transmit wavelengths up to about 7 micrometres, while some chalcogenide glasses transmit as far as 18 micrometres—properties that make them transparent into the middle infrared region.

Glass to which certain metallic oxides have been added will absorb wavelengths corresponding to certain colours and let others pass, thus appearing tinted to the eye. For instance, cobalt gives an intense blue tint to glass, chromium generally gives green, and manganese imparts purple.

Photosensitivity

In some glasses containing small amounts of cerium oxide and ions of copper, silver, or gold, exposure to ultraviolet radiation causes the oxidation of cerium and the reduction of the latter elements to the metallic state. Upon subsequent heating, the metal nuclei grow, or “strike,” developing strong colours (red for copper and gold, yellow for silver) in the ultraviolet-exposed regions of the glass. This technique has been used to produce “three-dimensional photographs,” but a more recent use is in microphotolithography for the production of complex electronic circuits.

Traditional photochromic eyeglasses are generally alkali boroaluminosilicates with 0.01 to 0.1 percent silver halide and a small amount of copper. Upon absorption of light, the silver ion reduces to metallic silver, which nucleates to form colloids about 120 angstroms in size. This is small enough to keep the glass transparent, but the colloids are dense enough to make the glass look gray or brown. In photochromic eyeglasses, darkening is reversed either by the removal of light (optical bleaching) or by raising the temperature (thermal bleaching).

Refraction and reflection of light

A ray of light, on passing from one transparent medium to another transparent medium of different density, will be transmitted through the second medium with no loss of intensity or change in direction if it strikes the boundary between the two mediums at a right angle (90°). In geometric terms, the right angle at which the light ray meets the boundary is called the normal. If the light ray meets the boundary at an angle other than the normal, then it will be partially reflected back into the first medium and partially refracted, or deflected, in its path through the second medium. The extent to which the light is reflected and refracted depends on the relative densities of the two mediums involved (usually glass and air) and on the angle at which the light ray meets the boundary (known as the angle of incidence). As is shown in Figure 7, if the light ray meets the boundary at less than a certain critical angle (θ_c), most of the light will be refracted while a small amount is reflected. If it arrives at the boundary at the critical angle, then the emerging light will be of diminished intensity and will assume a direction parallel and close to the boundary; most of the light will be reflected. Finally, if the critical angle is exceeded, all of the light will be reflected back into the glass without suffering any loss of intensity. Known as total internal reflection, this phenomenon is widely exploited in single-lens reflex cameras and in fibre optics, in which light signals are piped for great distances before signal boosting is required.

Refraction can be expressed as a constant, known as the refractive index, which is derived mathematically from the ratio of the sine of the angle of incidence on the medium to the sine of the angle of refraction within the medium. The refractive index of a particular type of glass depends on its composition and on the wavelength of the light.

When glass is subjected to unequal stress components operating on perpendicular planes, it becomes birefringent (that is, doubly refracting). The resulting birefringence of a plane-polarized light can be measured by birefringence compensators such as a quartz wedge, and from this measurement the magnitude of the stresses can be estimated. In a polariscope fitted with a tint plate, stressed glass displays colours; the distribution of these colours also may be used for recognizing stress patterns during quality-control operations.