GARBILES, MARY JEAN D.

BSAE-4M

MATERIALS OF ENGINEERING

History of glass Naturally occurring glass, especially the volcanic glass obsidian, has been used by many Stone Age societies across the globe for the production of sharp cutting tools and, due to its limited source areas, was extensively traded. But in general, archaeological evidence suggests that the first true glass was made in coastal north Syria, Mesopotamia or Ancient Egypt. The earliest known glass objects, of the mid third millennium BCE, were beads, perhaps initially created as accidental byproducts of metal-working (slags) or during the production of faience, a pre-glass vitreous material made by a process similar to glazing. Glass remained a luxury material, and the disasters that overtook Late Bronze Age civilizations seem to have brought glass-making to a halt. Indigenous development of glass technology in South Asia may have begun in 1730 BCE. In ancient China, though, glassmaking seems to have a late start, compared to ceramics and metal work. In the Roman Empire, glass objects have been recovered across the Roman Empire in domestic, industrial and funerary contexts. Anglo-Saxon glass has been found across England during archaeological excavations of both settlement and cemetery sites. Glass in the Anglo-Saxon period was used in the manufacture of a range of objects including vessels, beads, windows and was even used in jewelry. The term glass developed in the late Roman Empire. It was in the Roman glassmaking center at Trier, now in modern Germany, that the late-Latin term glesum originated, probably from a Germanic word for a transparent, lustrous substance.

Glass is an amorphous (non-crystalline) solid material that exhibits a glass transition, which is the reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle state into a molten or rubber-like state. Glasses are typically brittle and can be optically transparent. Glass is a product obtained by the fusion of several inorganic substances, of which normally silica (SiO2) in the form of sand is the main one. The fused mass is cooled to ambient temperature at a rate fast enough to prevent crystallization, i.e., the molecules cannot arrange themselves into a crystalline pattern. The fast rate of cooling to prevent crystallization applies to transparent glasses, whereas in the case of translucent or opal glasses, the rate of cooling is such as to produce a pre-determined level of Crystal formation. soda-lime glass - most familiar type of glass, used for centuries in windows and drinking vessels. composed of about 75% silica (SiO2) plus sodium oxide (Na2O) from soda ash, lime (CaO), and several minor additives

However, the term glass is usually defined in a much wider sense, including every solid that possesses a non-crystalline (i.e. amorphous) structure and that exhibits a glass transition when heated towards the liquid state. In this wider sense, glasses can be made of quite different classes of materials: metallic alloys, ionic melts, aqueous solutions, molecular liquids, and polymers. For many applications (bottles, eyewear) polymer glasses (acrylic glass, polycarbonate, polyethylene terephthalate) are a lighter alternative to traditional silica glasses.

Silicate glass Silica (the chemical compound SiO2) is a common fundamental constituent of glass. In nature, vitrification of quartz occurs when lightning strikes sand, forming hollow, branching rootlike structures called fulgurite. Selected chronology of advances

1226 "Broad Sheet" first produced in Sussex 1330 "Crown Glass" first produced in Rouen, France. "Broad Sheet" also produced. Both were also supplied for export 1620 "Blown Plate" first produced in London. Used for mirrors and coach plates. 1678 "Crown Glass" first produced in London. This process dominated until the 19th century 1843 An early form of "Float Glass" invented by Henry Bessemer, pouring glass onto liquid tin. Expensive and not a commercial success. 1888 "Machine Rolled" glass introduced allowing patterns to be introduced 1898 "Wired Cast" glass invented by Pilkington for use where safety or security was an issue. 1959 "Float Glass" launched in UK. Invented by Sir Alistair Pilkington.

TYPES OF GLASSES A large variety of glass with different chemical and physical properties can be made by a suitable adjustment to chemical compositions. Further sections of this booklet deal with various glasses, including crystal and optical glasses of high refractive index and high lead contentment. Commercial Glasses The main constituent of practically all commercial glasses is sand. Sand by itself can be fused to produce glass but the temperature at which this can be achieved is about 1700oC. Adding other chemicals to sand can considerably reduce the temperature of fusion. The addition of sodium carbonate (Na2CO3), known as soda ash, in a quantity to produce a fused mixture of 75% silica (SiO2) and 25% of sodium oxide (Na2O), will reduce the temperature of fusion to about 800oC. However, a glass of this composition is water soluble and is known as water glass. In order to give the glass stability, other chemicals like calcium oxide (CaO) and magnesium oxide (MgO) are needed. The raw materials used for introducing CaO and MgO are their carbonates CaCO3 (limestone) and MgCO3 (dolomite), which when subjected to high temperatures give off carbon dioxide leaving the oxides in the glass. Most commercial glasses whether for containers, i.e. bottles and jars, flat glass for windows or for drinking glasses, have somewhat similar chemical compositions of: SiO2 (silica) Na2O 12% - 16% (sodium oxide) CaO 5% - 11% (calcium oxide) 1% - 3% MgO 70% - 74%

(magnesium oxide) Al2O3 1% - 3% (aluminum oxide) Within these very wide limits the composition is varied to suit a particular products and production method. The raw materials are carefully weighed and thoroughly mixed, as consistency of composition is of utmost importance. To the mixture of chemicals a further raw materials added - broken glass, called cullet. Cullet can come from factory rejects, it can be collected by the public in Bottle Banks or from the bottling industry. Almost any proportion of cullet can be added to the mix (known as batch), provided it is in the right condition, and green glass made from batch containing 95% of cullet is by no means uncommon. Although the glass collected by Bottle Banks may come from several manufacturer, it can be used by one of them, as container glass compositions have been harmonized to make this possible. It is, however, important that glass colors are not mixed and that the cullet is free from impurities, especially metals and ceramics. Flat glass is similar in composition to container glass except that it contains a higher proportion of magnesium oxide. Other types of glasses Glasses vary widely in their chemical make-up; indeed, there are very few element in the periodic table that have not been incorporated in a glass of some kind. However, most of the glasses produced commercially on a large scale may be classified into three main groups: soda-lime, lead and borosilicate, of which the first is by far the most common. Soda-lime glasses These are the most common commercial glasses and have been described in the previous chapter. The chemical and physical properties of soda-lime glasses make them suitable for a visible light and hence applications. The nominally colorless types transmit a very high percentage of visible light and hence have been used for windows since at least the time of the Romans. Soda-lime glass containers are virtually inert, and so cannot contaminate the contents inside or affect the taste. Their resistance to chemical attack from aqueous solutions is good enough to withstand repeated boiling(as in the case of preserving jars) without any significant changes in the glass surface. One of the main disadvantages of soda-lime is their relatively high thermal expansion. Silica does not expand very greatly when heated but the addition of soda has a dramatic effect in increasing the expansion rate and, in general, the higher the soda content of a glass, the poorer will be its resistance to sudden changes of temperature (thermal shock). Thus, care is needed when soda-lime containers are filled with hot liquids to prevent breakages due to rapid thermal expansion. Lead glasses The use of lead oxide instead of calcium oxide, and of potassium oxide instead of all or most of the sodium oxide, gives the type of glass commonly known as lead crystal. The traditional English full lead crystal contains at least 30% lead oxide (PbO) but any glass containing at least 24% PbO can be legitimately described as lead crystal according to the relevant EEC directive. Glasses of the same type, but containing less than 24% PbO, are known simply as crystal glasses, some or all of the lead being replaced in these compositions by varying

amounts of the oxides of barium, zinc and potassium. Lead glasses have a high refractive index and relatively soft surface so that they are easy to decorate by grinding, cutting, engraving. The overall effect of cut crystal is the brilliance of the two. Glasses with even higher lead oxide contents (typically 65%) may be used as radiation shielding glasses because f the well-known ability of lead to absorb gamma rays and other forms of harmful radiation. Borosilicate glasses As the name implies, borosilicate glasses, the third major group, are composed mainly of silica (70-80%) and boric oxide (7-13%) with smaller amounts of the alkalis (sodium and potassium oxides) and aluminum oxide. They are characterized by the relatively low alkali content and consequently have good chemical durability and thermal shock resistance. Thus they are permanently suitable for process plants in the chemical industry, for laboratory apparatus, for ampoules and other pharmaceutical containers, for various high intensity lighting applications and as glass fibers for textile and plastic reinforcement. In the home they are familiar in the form of ovenware and other heat-resisting ware, possibly better known under the trade name of the first glass of this type to be placed on the consumer market- Pyrex. Special glasses Glasses with specific properties may be devised to meet almost any imaginable requirement, the main restriction normally being the commercial considerations, i.e., whether the potential market is large enough to justify the development and manufacturing costs. For many specialized applications in chemistry, pharmacy, the electrical and electronics industries, optics, the construction and lighting industries, glass, or the comparatively new family of materials known as glass ceramics, may be the only practical material for the engineer to use. Vitreous silica As mentioned previously, silica glass or vitreous silica is of considerable technical importance. However, the fact that temperature above 1500oC are necessary in the melting makes the transparent variety (often known as fused quartz or quartz glass) expensive and difficult to produce. The less expensive alternative for many applications is fused silica, which is melted at somewhat lower temperatures; in this case small gas bubbles remain in the final product which is therefore not transparent. Another substitute for vitreous silica can be produced by melting a suitable borosilicate glass and then heating it at around 600oC until it separates into two phases. The alkali-borate phase may be leached out with acids, leaving a 96% silica phase with open pores of controllable size which can be converted into clear glass. Porous glasses of this kind, commonly known as Vycor, from the first commercial version produced by Corning Glass Works Ltd, may be used as membranes for filtration purposes and for certain biological applications. Aluminosilicate glasses A small, but important group of glasses is that known as aluminosilicate, containing some 20% aluminum oxide (alumina-Al2O3) often including calcium oxide, magnesium oxide and boric oxide in relatively small amounts, but with only very small amounts of soda or potash. They tend to require higher melting temperatures than borosilicate glasses and are difficult to work, but have the merit of being able to withstand high temperatures and having good resistance to thermal shock. Typical applications include combustion tubes, gauge glasses for high pressure

steam boilers, and in halogen-tungsten lamps capable of operating at temperature as high as 750oC.

Alkali-barium silicate glasses In normal operation, a television produces X-rays which need to be absorbed by the various glass components. This protection is afforded by glasses with minimum amounts of heavy oxides (lead, barium or strontium). Lead glasses are commonly used for the funnel and neck of the tube, while glasses containing barium are usually employed for the face or panel. Borate glasses There is a range of glasses, containing little or no silica, that can be used for soldering glasses, metals or ceramics at relatively low temperatures. When used to solder other glasses, the solder glass needs to be fluid at temperatures (450o - 550oC) well below that at which the glass to be sealed will deform. Some solder glasses do not crystallize or denitrify during the soldering process and thus the mating surfaces can be reset or separated; these are usually lead borate glasses containing 60-90% PbO with relatively small amounts of silica and alumina to improve the chemical durability. Another group consists of glasses that are converted partly into crystalline materials when the soldering temperature is reached, in which case the joints can be separated only by dissolving the layer of solder by chemical means. Such denitrifying solder glasses are characterized by continuing up to about 25% zinc oxide. Glasses of a slightly different composition (zinc-silicoborate glasses) may also be used for protecting silicon semi-conductor components against chemical attack and mechanical damage. Such glasses must contain no alkalis (which can influence the semi-conducting properties of the silicon) and should be compatible with silicon in terms of thermal expansion. These materials, known as passivation glasses, have assumed considerable importance with the progress made in microelectronics technology in recent years that has made the concept of the "silicon chip" familiar to all. Phosphate glasses Most types of glass are good insulators at room temperature, although those with a substantial alkali content may well be good conductors in the molten state. This is because the conductivity depends mainly on the ability of the alkali ions in the glass to migrate in an electric field. However, some glasses that do not contain alkalis conduct electrons which jump from one ion to another. These are known as semi-conducing oxide glasses and are used particularly in the construction of secondary electron multipliers. Typically they consist of mixtures of vanadium pentoxide (V2O5) and phosphorous pentoxide (P2O5). Chalcogenide glasses Similar semi conductor effects are also characteristic of a series of glasses which can be made without the presence of oxygen (non-oxide glasses). These may be composed of one or more elements of the sulphur group in the Periodic Table (called chalcogens, from the Greek word for sulphur) combined with arsenic, antimony, germanium and/or the halide (fluorine, chlorine, bromine, iodine). Some of them have potential use as infra-red transmitting materials and as

switching devices in computer memories because their conductivity changes abruptly when particular threshold voltage values are exceeded, but most have extremely low softening points and much poorer chemical durability than more conventional glasses. Glass Ceramics An essential feature of glass structure is that it does not contain crystals. However, by deliberately stimulating crystal growth in appropriate glasses it is possible to produce a range of materials with a controlled amount of crystallization so that they can combine many of the best features of ceramics and glass. Some of these "glass ceramics" formed typically from lithium aluminosilicate glasses, are extremely resistant to thermal stock and have found several applications where this property if important, including cooker hobs, cooking ware, windows for gas or coal fires, mirror substrates for astronomical telescopes and missile nose cones.

Ingredients Quartz sand (silica) is the main raw material in commercial glass production While fused quartz (primarily composed of SiO2) is used for some special applications, it is not very common due to its high glass transition temperature of over 1200 C (2192 F). Normally, other substances are added to simplify processing. One is sodium carbonate (Na2CO3, "soda"), which lowers the glass transition temperature. However, the soda makes the glass water soluble, which is usually undesirable, so lime (calcium oxide[CaO], generally obtained from limestone), some magnesium oxide (MgO) and aluminium oxide (Al2O3) are added to provide for a better chemical durability. The resulting glass contains about 70 to 74% silica by weight and is called a soda-lime glass. Soda-lime glasses account for about 90% of manufactured glass. Most common glass contains other ingredients added to change its properties. Lead glass or flint glass is more 'brilliant' because the increased refractive index causes noticeably more specular reflection and increased optical dispersion. Adding barium also increases the refractive index. Thorium oxide gives glass a high refractive index and low dispersion and was formerly used in producing high-quality lenses, but due to its radioactivity has been replaced by lanthanum oxide in modern eye glasses.[citation needed] Iron can be incorporated into glass to absorb infrared energy, for example in heat absorbing filters for movie projectors, while cerium(IV) oxide can be used for glass that absorbs UV wavelengths. The following is a list of the more common types of silicate glasses, and their ingredients, properties, and applications: 1. Fused silica glass, vitreous silica glass: silica (SiO2). Has very low thermal expansion, is very hard and resists high temperatures (10001500 C). It is also the most resistant against weathering (alkali ions leaching out of the glass, while staining it). It is used for high temperature applications such as furnace tubes, melting crucibles, etc. 2. Soda-lime-silica glass, window glass: silica 72% + sodium oxide (Na2O) 14.2% + magnesia (MgO) 2.5% + lime (CaO) 10.0% + alumina (Al2O3) 0.6%. Is transparent, easily formed and most suitable for window glass. It has a high thermal expansion and poor resistance to heat (500600 C). Used for windows, containers, light bulbs, tableware.

3. Sodium borosilicate glass, Pyrex: silica 81% + boric oxide (B2O3) 12% + soda (Na2O) 4.5% + alumina (Al2O3) 2.0%. Stands heat expansion much better than window glass. Used for chemical glassware, cooking glass, car head lamps, etc. Borosilicate glasses (e.g. Pyrex) have as main constituents silica and boron oxide. They have fairly low coefficients of thermal expansion (7740 Pyrex CTE is 3.25106/C as compared to about 9106/C for a typical soda-lime glass), making them more dimensionally stable. The lower CTE also makes them less subject to stress caused by thermal expansion, thus less vulnerable to cracking from thermal shock. They are commonly used for reagent bottles, optical components and household cookware. 4. Lead-oxide glass, crystal glass: silica 59% + soda (Na2O) 2.0% + lead oxide (PbO) 25% + potassium oxide (K2O) 12% + alumina 0.4% + zinc oxide (ZnO) 1.5%. Has a high refractive index, making the look of glassware more brilliant (crystal glass). It also has a high elasticity, making glassware 'ring'. It is also more workable in the factory, but cannot stand heating very well. 5. Aluminosilicate glass: silica 57% + alumina 16% + boric oxide (B2O3) 4.0% + barium oxide (BaO) 6.0% + magnesia 7.0% + lime 10%. Extensively used for fiberglass, used for making glass-reinforced plastics (boats, fishing rods, etc.). Also for halogen bulb glass. 6. Oxide glass: alumina 90% + germanium oxide (GeO2) 10%. Extremely clear glass, used for fiber-optic wave guides in communication networks. Light loses only 5% of its intensity through 1 km of glass fiber. Another common glass ingredient is "cullet" (recycled glass). The recycled glass saves on raw materials and energy; however, impurities in the cullet can lead to product and equipment failure. Fining agents such as sodium sulfate, sodium chloride, or antimony oxide may be added to reduce the number of air bubbles in the glass mixture. Glass batch calculation is the method by which the correct raw material mixture is determined to achieve the desired glass composition. Contemporary production Following the glass batch preparation and mixing, the raw materials are transported to the furnace. Soda-lime glass for mass production is melted in gas fired units. Smaller scale furnaces for specialty glasses include electric melters, pot furnaces, and day tanks. After melting, homogenization and refining (removal of bubbles), the glass is formed. Flat glass for windows and similar applications is formed by the float glass process, developed between 1953 and 1957 by Sir Alastair Pilkington and Kenneth Bickerstaff of the UK's Pilkington Brothers, who created a continuous ribbon of glass using a molten tin bath on which the molten glass flows unhindered under the influence of gravity. The top surface of the glass is subjected to nitrogen under pressure to obtain a polished finish. Container glass for common bottles and jars is formed by blowing and pressing methods. Further glass forming techniques are summarized in the table Glass forming techniques. Once the desired form is obtained, glass is usually annealed for the removal of stresses. Surface treatments, coatings or lamination may follow to improve the chemical durability (glass container coatings, glass container internal treatment), strength (toughened glass, bulletproof glass, windshields), or optical properties (insulated glazing, anti-reflective coating). Architecture The use of glass in buildings is a transparent feature to allow light to enter into rooms and floors, illuminating enclosed spaces and framing an exterior view through a window. It is also a material for internal partitions and external cladding.

In the laboratory New chemical glass compositions or new treatment techniques can be initially investigated in smallscale laboratory experiments. The raw materials for laboratory-scale glass melts are often different from those used in mass production because the cost factor has a low priority. In the laboratory mostly pure chemicals are used. Care must be taken that the raw materials have not reacted with moisture or other chemicals in the environment (such as alkali or alkaline earth metal oxides and hydroxides, or boron oxide), or that the impurities are quantified (loss on ignition). Evaporation losses during glass melting should be considered during the selection of the raw materials, e.g., sodium selenite may be preferred over easily evaporating SeO2. Also, more readily reacting raw materials may be preferred over relatively inert ones, such as Al(OH)3 over Al2O3. Usually, the melts are carried out in platinum crucibles to reduce contamination from the crucible material. Glass homogeneity is achieved by homogenizing the raw materials mixture (glass batch), by stirring the melt, and by crushing and re-melting the first melt. The obtained glass is usually annealed to prevent breakage during processing. In order to make glass from materials with poor glass forming tendencies, novel techniques are used to increase cooling rate, or reduce crystal nucleation triggers. Examples of these techniques include aerodynamic levitation (cooling the melt whilst it floats on a gas stream), splat quenching (pressing the melt between two metal anvils) and roller quenching (pouring the melt through rollers). Network glasses A CD-RW (CD). Chalcogenide glassesform the basis of re-writable CD and DVD solid-state memory technology. Some glasses that do not include silica as a major constituent may have physico-chemical properties useful for their application in fiber optics and other specialized technical applications. These include fluoride glasses, aluminosilicates, phosphate glasses, borate glasses, and chalcogenide glasses. There are three classes of components for oxide glasses: network formers, intermediates, and modifiers. The network formers (silicon, boron, germanium) form a highly cross-linked network of chemical bonds. The intermediates (titanium, aluminium, zirconium, beryllium, magnesium, zinc) can act as both network formers and modifiers, according to the glass composition. The modifiers (calcium, lead, lithium, sodium, potassium) alter the network structure; they are usually present as ions, compensated by nearby non-bridging oxygen atoms, bound by one covalent bond to the glass network and holding one negative charge to compensate for the positive ion nearby. Some elements can play multiple roles; e.g. lead can act both as a network former (Pb 4+ replacing Si4+), or as a modifier. The presence of non-bridging oxygens lowers the relative number of strong bonds in the material and disrupts the network, decreasing the viscosity of the melt and lowering the melting temperature. The alkali metal ions are small and mobile; their presence in glass allows a degree of electrical conductivity, especially in molten state or at high temperature. Their mobility, however, decreases the chemical resistance of the glass, allowing leaching by water and facilitating corrosion. Alkaline earth ions, with their two positive charges and requirement for two non-bridging oxygen ions to compensate for their charge, are much less mobile themselves and also hinder diffusion of other ions, especially

the alkalis. The most common commercial glasses contain both alkali and alkaline earth ions (usually sodium and calcium), for easier processing and satisfying corrosion resistance. Corrosion resistance of glass can be achieved by dealkalization, removal of the alkali ions from the glass surface by reaction with e.g. sulfur or fluorine compounds. Presence of alkaline metal ions has also detrimental effect to the loss tangent of the glass, and to its electrical resistance; glasses for electronics (sealing, vacuum tubes, lamps...) have to take this in account. Addition of lead (II) oxide lowers melting point, lowers viscosity of the melt, and increases refractive index. Lead oxide also facilitates solubility of other metal oxides and therefore is used in colored glasses. The viscosity decrease of lead glass melt is very significant (roughly 100 times in comparison with soda glasses); this allows easier removal of bubbles and working at lower temperatures, hence its frequent use as an additive in vitreous enamels and glass solders. The high ionic radius of the Pb2+ ion renders it highly immobile in the matrix and hinders the movement of other ions; lead glasses therefore have high electrical resistance, about two orders of magnitude higher than soda-lime glass (108.5 vs 106.5 Ohmcm, DC at 250 C). For more details, see lead glass. Addition of fluorine lowers the dielectric constant of glass. Fluorine is highly electronegative and attracts the electrons in the lattice, lowering the polarizability of the material. Such silicon dioxidefluoride is used in manufacture of integrated circuits as an insulator. High levels of fluorine doping lead to formation of volatile SiF2O and such glass is then thermally unstable. Stable layers were achieved with dielectric constant down to about 3.53.7. Amorphous metals Samples of amorphous metal, with millimeter scale In the past, small batches of amorphous metals with high surface area configurations (ribbons, wires, films, etc.) have been produced through the implementation of extremely rapid rates of cooling. This was initially termed "splat cooling" by doctoral student W. Klement at Caltech, who showed that cooling rates on the order of millions of degrees per second is sufficient to impede the formation of crystals, and the metallic atoms become "locked into" a glassy state. Amorphous metal wires have been produced by sputtering molten metal onto a spinning metal disk. More recently a number of alloys have been produced in layers with thickness exceeding 1 millimeter. These are known as bulk metallic glasses (BMG). Liquidmetal Technologies sell a number of zirconium-based BMGs. Batches of amorphous steel have also been produced that demonstrate mechanical properties far exceeding those found in conventional steel alloys. In 2004, NIST researchers presented evidence that an isotropic non-crystalline metallic phase (dubbed "q-glass") could be grown from the melt. This phase is the first phase, or "primary phase," to form in the Al-Fe-Si system during rapid cooling. Interestingly, experimental evidence indicates that this phase forms by a first-order transition. Transmission electron microscopy (TEM) images show that the q-glass nucleates from the melt as discrete particles, which grow spherically with a uniform growth rate in all directions. The diffraction pattern shows it to be an isotropic glassy phase. Yet there is a nucleation barrier, which implies an interfacial discontinuity (or internal surface) between the glass and the melt. Electrolytes Electrolytes or molten salts are mixtures of different ions. In a mixture of three or more ionic species of dissimilar size and shape, crystallization can be so difficult that the liquid can easily be supercooled into a glass. The best studied example is Ca0.4K0.6(NO3)1.4.

Aqueous solutions Some aqueous solutions can be supercooled into a glassy state, for instance LiCl: RH2O in the composition range 4<R<8. Molecular liquids A molecular liquid is composed of molecules that do not form a covalent network but interact only through weak van der Waals forces or through transient hydrogen bonds. Many molecular liquids can be supercooled into a glass; some are excellent glass formers that normally do not crystallize. A widely known example is sugar glass. Under extremes of pressure and temperature solids may exhibit large structural and physical changes that can lead to polyamorphic phase transitions. In 2006 Italian scientists created an amorphous phase of carbon dioxide using extreme pressure. The substance was named amorphous carbonia(aCO2) and exhibits an atomic structure resembling that of silica. Polymers Important polymer glasses include amorphous and glassy pharmaceutical compounds. These are useful because the solubility of the compound in greatly increased when it is amorphous compared to the same crystalline composition. Many emerging pharmaceuticals are practically insoluble in their crystalline forms. According to the Eastman Company, "[t]he Glass Polymer family of cosmetic materials offers innovative design and application possibilities. It is a compelling alternative to traditional polymers and can be used where glass falls short. Colloidal glasses Concentrated colloidal suspensions may exhibit a distinct glass transition as function of particle concentration or density. Glass-ceramics A high-strength glass-ceramic cooktop with negligible thermal expansion. Glass-ceramic materials share many properties with both non-crystalline glass and crystalline ceramics. They are formed as a glass, and then partially crystallized by heat treatment. For example, the microstructure of whiteware ceramics frequently contains both amorphous and crystalline phases. Crystalline grains are often embedded within a noncrystalline intergranular phase of grain boundaries. When applied to whiteware ceramics, vitreousmeans the material has an extremely low permeability to liquids, often but not always water, when determined by a specified test regime. The term mainly refers to a mix of lithium and aluminosilicates that yields an array of materials with interesting thermomechanical properties. The most commercially important of these have the distinction of being impervious to thermal shock. Thus, glass-ceramics have become extremely useful for countertop cooking. The negative thermal expansion coefficient (CTE) of the crystalline ceramic phase can be balanced with the positive CTE of the glassy phase. At a certain point (~70%

crystalline) the glass-ceramic has a net CTE near zero. This type of glass-ceramic exhibits excellent mechanical properties and can sustain repeated and quick temperature changes up to 1000 C. The amorphous structure of glassy silica (SiO2) in two dimensions. No long-range order is present, although there is local ordering with respect to the tetrahedral arrangement of oxygen (O) atoms around the silicon (Si) atoms. Structure As in other amorphous solids, the atomic structure of a glass lacks any long-range translational periodicity. However, due to chemical bonding characteristics glasses do possess a high degree of short-range order with respect to local atomic polyhedra. Comparison with supercooled liquid In physics, the standard definition of a glass (or vitreous solid) is a solid formed by rapid melt quenching.[33][34][35][36][37] However, the term glass is often used to describe any amorphous solid that exhibits a glass transition temperature Tg. If the cooling is sufficiently rapid (relative to the characteristic crystallization time) then crystallization is prevented and instead the disordered atomic configuration of the supercooled liquid is frozen into the solid state at Tg. Generally, the structure of a glass exists in a metastable state with respect to its crystalline form, although in certain circumstances, for example in atactic polymers, there is no crystalline analogue of the amorphous phase. Some people consider glass to be a liquid due to its lack of a first-order phase transition where certain thermodynamic variables such as volume,entropy and enthalpy are discontinuous through the glass transition range. However, the glass transition may be described as analogous to a secondorder phase transition where the intensive thermodynamic variables such as the thermal expansivity and heat capacity are discontinuous. Despite this, the equilibrium theory of phase transformations does not entirely hold for glass, and hence the glass transition cannot be classed as one of the classical equilibrium phase transformations in solids. Glass is an amorphous solid. It exhibits an atomic structure close to that observed in the supercooled liquid phase but displays all the mechanical properties of a solid. The notion that glass flows to an appreciable extent over extended periods of time is not supported by empirical research or theoretical analysis (see viscosity of amorphous materials). Laboratory measurements of room temperature glass flow do show a motion consistent with a material viscosity on the order of 10 171018 Pa s. Although the atomic structure of glass shares characteristics of the structure in a supercooled liquid, glass tends to behave as a solid below its glass transition temperature. A supercooled liquid behaves as a liquid, but it is below the freezing point of the material, and in some cases will crystallize almost instantly if a crystal is added as a core. The change in heat capacity at a glass transition and a melting transition of comparable materials are typically of the same order of magnitude, indicating that the change in active degrees of freedom is comparable as well. Both in a glass and in a crystal it is mostly only the vibrational degrees of freedom that remain active, whereas rotational and translationalmotion is arrested. This helps to explain why both crystalline and non-crystalline solids exhibit rigidity on most experimental time scales. Behavior of antique glass The observation that old windows are sometimes found to be thicker at the bottom than at the top is often offered as supporting evidence for the view that glass flows over a timescale of centuries, the assumption being that the glass was once uniform but has flowed to its new shape, which is a

property of liquid. However, this assumption is incorrect; once solidified, glass stops flowing. The reason for the observation is that in the past, when panes of glass were commonly made by glassblowers, the technique used was to spin molten glass so as to create a round, mostly flat and even plate (the crown glass process, described above). This plate was then cut to fit a window. The pieces were not, however, absolutely flat; the edges of the disk became a different thickness as the glass spun. When installed in a window frame, the glass would be placed with the thicker side down both for the sake of stability and to prevent water accumulating in the leadcames at the bottom of the window. Occasionally such glass has been found thinner side down or thicker on either side of the window's edge, the result of carelessness during installation. Mass production of glass window panes in the early twentieth century caused a similar effect. In glass factories, molten glass was poured onto a large cooling table and allowed to spread. The resulting glass is thicker at the location of the pour, located at the center of the large sheet. These sheets were cut into smaller window panes with nonuniform thickness, typically with the location of the pour centered in one of the panes (known as "bull's-eyes") for decorative effect. Modern glass intended for windows is produced as float glass and is very uniform in thickness. Several other points can be considered that contradict the "cathedral glass flow" theory: Writing in the American Journal of Physics, materials engineer Edgar D. Zanotto states "... the predicted relaxation time for GeO2 at room temperature is 1032 years. Hence, the relaxation period (characteristic flow time) of cathedral glasses would be even longer."(1032 years is many times longer than the estimated age of the Universe.) If medieval glass has flowed perceptibly, then ancient Roman and Egyptian objects should have flowed proportionately more but this is not observed. Similarly, prehistoric obsidian blades should have lost their edge; this is not observed either (although obsidian may have a different viscosity from window glass). If glass flows at a rate that allows changes to be seen with the naked eye after centuries, then the effect should be noticeable in antique telescopes. Any slight deformation in the antique telescopic lenses would lead to a dramatic decrease in optical performance, a phenomenon that is not observed. There are many examples of centuries-old glass shelving that has not bent, even though it is under much higher stress from gravitational loads than vertical window glass. The above does not apply to materials that have a glass transition temperature close to room temperature, such as certain plastics used in daily life like polystyrene and polypropylene. Physical properties Optical properties Glass is in widespread use largely due to the production of glass compositions that are transparent to visible wavelengths of light. In contrast, polycrystalline materials do not in general transmit visible light. The individual crystallites may be transparent, but their facets (grain boundaries) reflect or scatter light resulting in diffuse reflection. Glass does not contain the internal subdivisions associated with grain boundaries in polycrystals and hence does not scatter light in the same manner as a polycrystalline material. The surface of a glass is often smooth since during glass formation the molecules of the supercooled liquid are not forced to dispose in rigid crystal geometries and can follow surface tension, which imposes a microscopically smooth surface. These properties, which give glass its clearness, can be retained even if glass is partially light-absorbing i.e. colored. Glass has the ability to refract, reflect, and transmit light following geometrical optics, without scattering it. It is used in the manufacture of lenses and windows. Common glass has a refraction index around 1.5. According to Fresnel equations, the reflectivity of a sheet of glass is about 4% per

surface (at normal incidence in air), and the transmissivity of one element (two surfaces) is about 90%. Glass also finds application in optoelectronics e.g., for light-transmitting optical fibers. COLOURS Unless the raw materials are very pure, glass made by mixing and heating sand, soda ash and limestone will normally be green, the depth of the colorants present in the raw materials. a sand containing as little as one-thousandth part of iron oxide will give normal soda-lime glass, used for windows and glass containers, a greenish tint. For many products, instead of using high purity (and thus expensive) raw materials, glass manufacturers may decolorize the glass by adding minute amounts of other colorants which produce complementary colors to green so that the finished articles appear colorless. Thus selenium (which gives a pink color) and cobalt (which gives blue) can be added to soda-lime glass to offset the effect of the green or yellow due to the iron and this is done in the manufacture of glass containers. Nickel may be used similarly in the decolorizing of lead crystal glass. Different additions may produce different colored glasses, the range of possible colors being almost infinite. Some of the most frequently used colorants and the colors they produce are listed below. The color depends on the state of oxidation of the colorant, the type of glass in which it is used, and thermal treatment. COLORANT Iron Manganese Chromium Vanadium Copper Cobalt Nickel Uranium Titanium Neodymium Praseodymium Cerium Carbon & Sulphur Cadmium Sulphide Antimony Sulphide GLASS COLOUR/S Green, brown, blue Purple Green, yellow, pink Green, blue, grey Blue, green, red Blue, green, pink Yellow, purple Yellow, brown, green Purple, brown Purple Green Yellow Amber, brown Yellow Red

Selenium Gold

Pink, red Red

The use of large amounts of several different colorants will tend to produce black glasses. Opaque or opal glasses can be produced by the addition of appropriate amounts of fluoride or phosphate compounds, which produce crystal growth, known in the glass industry as devitirification. Color Common soda-lime float glass appears green in thick sections because of Fe2+impurities. Studio glass or art glass often includes multiple colors, which increases the difficulty of production, as each color has different chemical and physical properties when molten. Color in glass may be obtained by addition of electrically charged ions (or color centers) that are homogeneously distributed, and by precipitation of finely dispersed particles (such as in photochromic glasses). Ordinary soda-lime glass appears colorless to the naked eye when it is thin, althoughiron(II) oxide (FeO) impurities of up to 0.1 wt% produce a green tint, which can be viewed in thick pieces or with the aid of scientific instruments. Further FeO and Cr2O3 additions may be used for the production of green bottles. Sulfur, together with carbon and iron salts, is used to form iron polysulfides and produce amber glass ranging from yellowish to almost black. A glass melt can also acquire an amber color from a reducing combustion atmosphere. Manganese dioxide can be added in small amounts to remove the green tint given by iron(II) oxide. When used in art glass orstudio glass glass is colored using closely guarded recipes that involve specific combinations of metal oxides, melting temperatures and 'cook' times. Most colored glass used in the art market is manufactured in volume by vendors who serve this market although there are some glass makers with the ability to make their own color from raw materials. ~ Glass Properties, Composition & Uses ~ Making Glass Method of Specific Qualities Manufacture Relatively cheap when mass produced. Resistant to mechanical shock, capable of being filled at very fast rates. Some bottling plants fill in excess of 1000 bottles per minute. Can be re-used and recycled. Can be sterilized at high temperatures. inert, do not impart taste or toxic substances.

Product

Typical Formula

Soda-lime silica Approximate composition: SiO2 Na2O CaO Al2O3 % 74 14 11 1

Glass Containers Bottles & Jars

Automatically blown at high speeds.

Flat Glass

1. Relatively cheap. 2. Can be toughened. 3. Weather resistant. 4. Can be coated.

Soda-lime silica Approximate composition: Float process. Cast and rolled. SiO2 Na2O CaO Al2O3 MgO % 71 16 9 1 3

Domestic Glassware for everyday use in home and catering

1. Pleasant appearance. 2. Ability to stand up to constant use. 3. Does not affect contents

Soda-lime silica Mouth blown, Approximate composition: pressed or fully % % automatic mass SiO2 74 Al2O3 3 produced. Na2O 16 K2O 1 CaO 5 B2O3 1 MgO 3

Radiation Shielding

High density to absorb radiation.

Extrusion and casting can be ground and polished to optical precision.

Soda-lime silica Approximate composition: SiO2 PbO K2O % 3 1 1

Soda-lime silica Borosilicate Thermometer Tubing Thermal stability over a wide temperature range, retaining transparency. Automatic or hand drawing. Lead glass Depending on temperature

range required

Laboratory Glassware

High chemical durability. Low thermal expansion.

Lampworking (made from Mainly Borosilicate or tubing by heating fused silica for extra low and skilful expansion coefficient manipulation). Mouth and automatic blowing. Sintering.

Full Lead Crystal Domestic Glassware

1. Extra suitable for artistic hand shaping and mouth blowing. 2. Brilliant finish, attractive when Hand made by full or empty. skilled craftsmen. 3. Comparatively soft - easy to cut and polish or engrave.

Lead glass Approximate composition: SiO2 PbO K2O % 3 1 1

Heat Resistant Oven to Table Ware

Borosilicate glass 1. Resistant to Approximat thermal shock. e 2. Attractive. composition 3. Easy to clean. Automatically : 4. Can be used in pressed or blown. % % microwave ovens. SiO2 80 Na2O 4.5 B2O3 12 Al2O3 5

Optical Glass

1. Wide range of refractive indices. 2. Wide range of dispersion coefficients. 3. Perfect

Extrusion and pressing, then ground and polishing.

While range of compositions Depends on application

homogeneity. 4. Complete transparency.

Electrical Components: cathode-ray tubes, capacitors and resistors, computer components, printed circuits

Good dielectric properties. Low electrical losses over a wide range of temperatures. High operating temperatures.

Blowing. Drawing - in rod form and in sheets. Sintering and Pressing - glass is ground to fine grains and then is subsequently pressed into required shape and then fired. Wide range of compositions

Glass Building Blocks

Resistant to normal temperature changes. Resistant to atmospheric conditions. Mechanical strength. Attractive. Translucent.

Automatic pressing - pressed in halves and then fused together

Soda-lime silica glass Similar to flat glass

flame drawing - velocity of flames draws particles of glass Ballotini: minute glass High reflective up tower and as spheres (1-60 properties: mixed with the softened microns) which reflect paint for road signs glass falls on the light and cinema screens. outside, spheres are formed by surface tension effects.

Soda-lime silica glass Similar to flat glass

High strength-toweight ratio. Resistant to attack by corrosive substances. Resistant to high temperature. Flame resistant. High electrical resistance.

Filament drawing. Continuous filament. White wool.

Soda lime silica and where resistance to weathering is necessary, a borosilicate glass is used, e.g.

Crown process. Soda-lime silica glass Can be woven into textiles or % % incorporated with SiO 54.5 B O 8.3 2 2 3 plastics to form Al O 14.5 Na 2 3 2O 0.5 insulating materials, boat CaO 22.0 hulls, car bodies, etc.

Glass Fibre

Economical to produce. Easy to manufacture by mass production methods.

Lighting Glassware 1. Electric Light Bulbs

Resistant to shock. Impermeable and inert to gas, vapor and liquid. Durable. Transparent or translucent.

Ribbon Machine - produces bulb at the rate of over 1,000 per minute. Blanks used in the manufacture of vacuum flasks are also produced by this machine

Soda lime silica glass SiO2 Al2O3 CaO MgO Na2O K2O % 72.5 1.3 6.5 3.0 15.9 0.3

Special glasses 2. Special Glasses Low electrical can be formed by (a) High pressure conductivity. using mercury vapor lamps Resistance to intense manufacturing chemical activity of mercury vapor. processes, or, in (b) Aircraft fire-warning some cases, Low melting point. sensors laminated onto ordinary glasses (c) Glass for High electricity i.e. sodium encapsulating electric conductivity. discharge lamps.

Wide range of compositions

components Low electrical conductivity. Resistance to intense chemical activity.

Electrical discharge 3. Tubing for *generates UV light fluorescent lighting which then causes fluorescent powder to emit visible light. High efficiency. Long life: 3,000 5,000 hours, i.e. about one year of continuous use.

Automatic Drawing

Soda lime silica glass SiO2 Al2O3 CaO MgO Na2O K2O B2O3 % 72.5 2.6 5.7 2.9 14.6 1.2 0.3

Resistant to high 4. Domestic and temperature. industrial shades Resistant to thermal and bulkhead lights: shock. inc. lenses for traffic lights, car lights and Resistant to railway signal lights weathering. Accurate and non fading color: subject to strict BS specifications.

Mouth blowing. Hand and automatic pressing depending on quantities required.

1. Soda-lime silica glass 2. Laminated with opal glass 3. Borosilicate glasses and opal glasses

GLASS MELTING FURNACES There are two types of glass melting furnaces. 1. Pot Furnaces are structures built of refractory materials in which there is no contact between the furnace and the glass. Glass is melted in several pots made of refractory materials which are resistant to glass attack at high temperatures. The pots are charged with a batch, which is melted over a number of hours and worked on a 24 or 18 hour cycle. An average pot can hold 600-700 Kg of glass. Pot furnaces are used where the glass is formed by hand and mouth blowing. One of the main advantages of this system is that several types of glasses can be melted at the same time. A pot can be used for about 30 melting cycles and thus produce between 18 and 21 tons of glass.

Fuel economy is normally achieved by recuperation, i.e., the pre-heating of combustion air by waste heat from the furnace exhaust gases. In this system the pre-heating of the combustion air is done by passing the air through metal tubes on the outside of which the exhaust gases flow towards the chimney. Thus the heat exchange is continuous. Electricity can also be used for melting. 2. Tank Furnaces are used where continuous flow of glass is needed to feed automatic glass forming machines. They are more economical in their use of fuel and are used mainly for the large scale production of containers, flat glass, electric bulbs, tubing and domestic machine made tableware. A large float glass furnace can have a capacity of 2,000 tons. A tank furnace consists of a bath, built of a very special high refractory material, which can resist chemical attack of molten glass at temperatures in excess of 1500oC and a superstructure where combustion takes place. The quality of refractory materials, used for building the bath, has improved to such an extent that whereas some 30 years ago, the life of a furnace was well below 2 years, it is now over 9 years. In order to achieve high melting temperatures and fuel economy, a regenerative or recuperative system is used. Both these systems utilize the waste heat of combustion for pre-heating the incoming combustion air. While in the recuperative system the heat exchange between the combustion air and waste gases is continuous, in the regenerative system the waste gases are passed through a large chamber packed with refractory bricks arranged in a pattern which permits free flow of the gases. The brickwork is heated by the waste gases and after having been heated for some 20 minutes, the direction of firing is reversed. Combustion air is passed through the chamber and the heat thus collected in the brickwork is used for pre-heating the combustion air. The firing is thus from right to left, normally for 20 minutes, during which time the right hand generator is heated and so there is a reversal of firing every 20 minutes. The cycle time can be changed for best heat exchange results and modern furnaces have computer managed control systems, which adjust the time of firing in each direction to achieve the best heat exchange conditions. Heavy fuel oil or natural gas is normally used for firing tank furnaces. Glass, being an electrical conductor at high temperature, can also be melted by electricity. However, electricity is far too expensive in the UK and is normally used to boost the output from a gas or oil fired furnace. Nevertheless, technological progress in electric melting has enabled the use of all electric glass melting furnaces even at the high cost of electricity. GLASS FORMING PROCESSES Like treacle and pitch, glass is fluid at high temperature and its fluidity decreases at the temperature is reduced. In other words its viscosity decreases as the temperature increases. Unlike water, which turns from liquid to a solid at a specific temperature, glass has no specific melting or freezing point but is gradually changed from a stiff solid to a liquid mass as the temperature is increased. It is this property of variable viscosity which is utilized in forming a mass of glass into articles of beauty or utility. Glass Blowing For nearly 2,000 years mouth blowing was the main method of forming glass articles. The last few years of the 19th century saw the beginnings of blowing glass by compressed air and the 20th century brought in the revolution of mechanization.

For mouth blowing, a hollow blowing-iron or pipe is dipped into a pot containing molten glass and the glass is gathered at the end of the pipe by rotating it, similarly to gathering treacle onto a spoon. The collected glass, known as the gather, cools to about 1000oC and is marvered (rolled on an iron slab) to form a parison. The parison is then manipulated by allowing it to elongate, re-heating it and blowing air into it to bring it into a shape which resembles the final article to be formed. It is then placed in an iron or wooden mould, which is kept wet by water, and the glass is blown to the final shape of the interior of the mould. There is no contact between the glass and the mould, due to the water being present, a cushion of steam forms a barrier preventing this. During the blowing the pipe is rotated continuously, thus preventing mould joints or other mould imperfections appearing in the glass. Semi Automatic Bottle Making Until the second half of the 19th century bottles were made by hand gathering, mouth blowing and finishing the neck, which was to receive a closure, by manual manipulation with simple tools. The mouth of the bottle, being made last, was known as the "finish". No way was discovered of imitating this process by semi-mechanical or mechanical means until it was realized that the only way was to make the "finish" first. The glass is thus gathered on a solid rod and is allowed to flow into a parison mould until sufficient glass is judged to have entered the mould. It is then cut off by means of hand shears. At the bottom of the parison mould is the "finish" with a plunger, which forms the opening into which compressed air is blown. A puff of compressed air blows the glass upwards against the sides of the parison mould and a plate at its top. Thus a parison, which is a thick walled bottle vaguely resembling the final product, is formed. The parison is removed from the mould and by absence of contact with the iron, the heat from the outer surface is no longer conducted away and the parison surface is re-heated. It is then transferred to the final mould and blown again and the parison surface is re-heated. It is then transferred to the final mould and blown again by compressed air to its final shape. The mould is opened, the bottle is removed and placed in a re-heating tunnel, called a lehr, for annealing. Semi-automatic bottle making has practically disappeared in the developed countries and has been replaced by fully automatic production. Making Glass Container by Semi-Automatic Process The gob is gathered by hand on an iron, and the correct amount of glass is dropped into a preliminary mould. Compressed air is introduced to form the neck of the article. The embryo shape (parison) is then transferred to the finishing mould in which the final shape is blown. Automatic Container Production The principle of automatic production is exactly the same as that previously described, except that instead of gathering the glass on an iron rod and allowing it to flow into the parison mould, gobs of glass of pre-determined shape and weight are formed above the parison mould and are allowed to drop into it.

Making Glass Containers by Automatic Process

The Blow and Blow Process

The machine which has almost replaced all others is the IS machine. It is not certain whether "IS" denotes its inventors, Ingle and Smith, or its main characteristic which is independent synchronized units with a synchronized gob distribution system each section. It can consist of several sections and 10 section machines are by no means uncommon. The machine can operate on blow and blow or press and blow principle and double gob production, i.e. delivery of two gobs of glass at the same time is quite common. Triple gob machines are also in existence. The machine is capable of producing more than 200 containers per minute. Flat Glass The main flat glass products are float glass for high quality glazing in homes, offices, hotels, shops, transport and public buildings glass for horticulture: wired glasses for fire resistance; patterned glass for privacy and decoration; and a wide range of glasses for environmental control and energy conservation.

Other flat glass products include toughened glass doors, suspended window assemblies, cladding glasses for the exterior of buildings, mirrors and diffuse reflection glass for reducing reflection on glazed pictures and instrument dials. The two manufacturing processes for producing flat glass in the UK are the float glass process and the rolled process. The Float Glass Process The float glass process, invented by Pilkington Brothers PLC and introduced in 1959, is now the principal method of producing flat glass throughout the world. The glass is held in a chemically controlled atmosphere at a high enough temperature (1000 C) for a long enough time for irregularities to melt out and for the surfaces to become flat and parallel. Because the surface of the molten tin is flat the glass becomes flat and the thickness of the ribbon, in the range 2.5 to 25mm, is controlled at this stage. The ribbon is cooled down while still advancing along the molten tin until the surfaces are hard enough (600 C) for it to be lifted onto the conveyor rollers without marking the bottom surface. The ribbon passes through the annealing lehr to the automatic warehouse where computers govern the cutting of the ribbon to match customer's orders. A large modern float glass plant will produce 5000 tons of glass per week. It operates continuously 24 hours a day, 365 days a year for several years. The glass produced has a uniform thickness and bright fire-polished surfaces without the need for grinding and polishing. The Rolled Glass Process The rolling process is used for the manufacture of patterned flat glass and wired glass. A continuous stream of molten glass is poured between water cooled rollers. Patterned glass is made in a single pass process in which glass flows to the rollers at a temperature of about 1050 C. The bottom cast iron or stainless steel roller is engraved with the negative of the pattern; the top roller is smooth. Thickness is controlled by adjustment of the gap between the rollers. The ribbon leaves the rollers at about 850 C and is supported over a series of water cooled steel rollers to the annealing lehr. After annealing the glass is cut to size. Wired glass is made in a double pass process. The process uses two independently driven pairs of water cooled forming rollers each fed with a separate flow of molten glass from a common melting furnace. The first pair of rollers produces a continuous ribbon of glass, half the thickness of the end product. This is overlaid with a wire mesh. A second feed of glass, to give a ribbon the same thickness as the first, is then added and, with the wire mesh "sandwiched", the ribbon passes through the second pair of rollers which form the final ribbon of wired glass. After annealing, the ribbon is cut by special cutting and snapping arrangements. Glass Fibers Glass in the form of fibers has found wide and varied applications in all kinds of industry. Its composition depends on the intended use. For building insulation and glass wool the type of glass used is normally soda-lime. For textiles, an alumino-borosilicate glass with very low sodium oxide content (E glass) is preferred because of its good chemical durability and high softening point. This is also the type of composition employed for the fibers used in the reinforcement of plastics, familiar for their application in protective helmets,

boats, piping, car chassis and many other articles. In recent years, great progress has been made in making optical fibers which can guide light and thus transmit images round corners. These fibers are applicable to endoscopes for examination of internal human organs, changeable traffic message signs now in common use on motorways for speed restriction warnings and communications technology for transmitting telephone conversations much more efficiently than copper cable. There are two broad groups of glass fiber products: continuous glass fiber which is used for the reinforcement of plastics, rubber and cement; and glass wool, which is used for thermal insulation and which is produced by the Crown process. Glass Fiber Manufacture Continuous glass fiber is a continuous strand, made up of a large number of individual filaments of glass. Molten glass is fed from the furnace or "tank" through a channel or "forehearth" to a series of bushings which contain over one thousand six hundred accurately dimensioned holes or "forming tips" in its base. A constant head of glass is maintained in the tank and forehearth and the temperature of the glass in the bushings is controlled to very fine limits. Fine filaments of glass are drawn mechanically downwards from the bushing tips at a speed of several thousand meters per minute, giving a filament diameter which may be as small as nine microns, or one tenth the diameter of a human hair. From the bushing the filaments run to a common collecting point where size is applied and they are subsequently brought together as bundles, or "strands", on a high speed winder. Glass fiber is produced in a range of filament diameters and strand dimensions to tight tolerances for different end uses. It is used to strengthen and stiffen thermosetting plastics, thermoplastics, nylon and polypropylene as well as inorganic matrices, such as gypsum. Glass Wool Manufacture Glass wool is made in the Crown process. From the forehearth of the "tank" a thick stream of glass flows by gravity from the bushing into a rapidly rotating alloy steel dish "Crown" which has several hundred fine holes round its periphery. The molten glass is thrown out through the holes by centrifugal force to form filaments which are further extended into fine fibers by a high velocity blast of hot gas. After being sprayed with a suitable bonding agent, the fibres are drawn by suction onto a horizontally moving conveyor positioned below the rotating dish. The mat of tangled fibers formed on the conveyor is carried through an oven which cures the bonding agent, then to trimmers and guillotines which cut the product to size. The mat may be further processed into rigid sections for pipe insulation. The mats are made into many products for heat and sound insulation in buildings, transport vehicles and domestic appliances.

Optical Fiber Manufacture Communications are increasingly based on eletro-optic systems in which telephones, television and computers are linked by fiber optic cables which carry information by laser light. Making glass optical fibers is a highly specialized aspect of glass manufacture. Optical fibers consist of two distinct glasses, core of highly refracting glass surrounded by a sheath of glass with lower refractive index between the two glasses, it is guided by total reflection at the core-sheath interface to the other end of the fiber. In theory, a wide range of glasses can be used as long as the difference in refractive index is appropriate but the higher the refractive index of the core relative to that of the sheath glass, the greater the carrying capacity of the fiber. A typical system available commercially comprises a germanium doped silica core and a borosilicate cladding. The aim in manufacture is to produce a fiber of glass which is so pure and free form defects that light inserted at one end will emerge at the other end a distance of 1 kilometer or more away. There are many manufacturing processes being used to produce cored fiber; two of these will illustrate the principles. All the processes require ultra-pure starting materials. Chemical vapor deposition - high silica glass fibers are prepared by chemical vapor deposition in which layers of SiO, are deposited to make a preform, either on the outside of a mould or on the inside of a fused silica tube. The layers are doped during the deposition to control the refractive index. The preform is then drawn to a rod and subsequently to a fiber of 100-125mm diameter. The surface is protected from damage by a plastic coating. The double crucible method - The double crucible uses purified glasses in separate crucibles in a controlled atmosphere furnace. Fiber drawn from the tip consists of a uniform core drawn from the central crucible and a cladding drawn from the outer crucible. Tubing Manufacture of Tubing Danner Process The Danner Process was developed for the continuous production of glass tubing and rod. Subject to equipment design the process can make tubing of 1.6mm to 66.5mm diameter and rods of 2.0mm to 20mm diameter at drawing rates of up to 400m a minute for the smaller sizes. Glass flows from a furnace forehearth in the form of a ribbon which falls on to the upper end of an inclined refractory sleeve carried on a rotating hollow shaft or blowpipe. The ribbon is wrapped around the sleeve to form a smooth layer of glass which flows down the sleeve and over the tip of the

shaft. Tubing is formed by blowing air through a blowpipe with a hollow tip and rods are made by using a solid tip on the shaft. The tubing is then drawn over a line of support rollers by a drawing machine situated up to 120m away. The dimensions of the tubing are determined as the glass cools through its setting point at the catenary or unsupported section between the blowpipe and the first line roller. A given range of size is based on the diameter of the refractory sleeve, and variations within the range are obtained by adjusting the temperature of the glass, the rate of flow, the pressure of the blowing air and the speed of the drawing machine. Manufacture of Tubing Vello Process The Vello process was a later development with a production capacity greater than that of the Danner process but based on a different principle. Glass flows from a furnace forehearth into a bowl in which a hollow vertical mandrel is mounted or a bell surrounded by an orifice ring. The glass flows through the annular space between the bell and the ring and travels over a line of rollers to a drawing machine up to 120m away. Tubing is made by blowing air through a bell with a hollow tip and rod is produced by using a bell with a solid tip. The dimensions of the tubing are controlled by the glass temperature, the rate of draw, the pressure of the blowing air and the relative dimensions of the bell and ring. Automatic Domestic Glassware Production The Westlake machine was developed for blowing bulbs for domestic lamps and radio valves at production rates of up to 75,000 a day (gross). It has since been adapted for making drinking glasses, including stemmed ware, at up to 55,000 a day (gross). The machine copies the action of a handblower in gathering glass from the furnace, forming a parison and blowing the article in a cast iron mould. Twelve pairs of spindles or blowpipes, together with their blowing air valves and past moulds, travel around a central column. The gathering equipment is carried on top of the column and sets of cams are fitted around the column to control the sequence of operations. Glass is gathered by vacuum into a pair of blank moulds and the pairs of blanks are transferred in turn to each pair of spindles. The spindles are rotated and swung down, and air is introduced to form each blank into a parison, controlling the profile and distribution of the glass before blowing the required shape in the wetted mould. The mould opens and the spindle jaws release the article which is then transferred to the stemming machine. Here the neck formed in the mould is reheated and stretched to the required length. The article then passes to the burn-off machine where oxygen-gas flames remove the "moil" or waste glass which was originally formed at the gathering position, and the finished piece is conveyed to the lehr for annealing. Electric Light Bulb Envelope Production The ribbon machine was developed for the high speed manufacture of bulbs for domestic lamps, auto lamps, vacuum flasks, etc. Its main feature is that glass travels through it in a straight line rather than on a rotary path as with the Westlake machines. Production rates in excess of 1000 a minute can be achieved.

From the furnace forehearth molten glass flows down between two rotating water cooled rollers and on to the Ribbon machine. On leaving the rollers the ribbon of glass is carried through the machine on a series of orifice plates, forming a continuous belt pierced with holes. As the ribbon moves forward, a continuous chain of blowheads does the glassblower's job for him. It blows the glass through the hole and the "blister" forms into a bulb inside a rotating mould which meets and closes around it from below. Still moving forward on the ribbon, the shaped bulb is released form its mould, cooled by air jets and then tapped off the ribbon to fall onto the scoops of a rotary turntable which tips it on to a conveyor belt. This carries it through an annealing lehr and air cooling to inspection and packing. The unused part of the ribbon passes direct to a cullet system for re-melting. Electric Light Bulb Envelope Manufacture Molten glass flows continuously between water cooled rollers and the ribbon so formed on orifice plates. Blowheads from above blow the glass through the holes in the plates. Moulds form below meet and close round these "blisters". The mould fall away revealing the formed bulbs which are cooled by air jets and tapperd off the ribbon. They fall into scoops on the rotary turntable which tip them onto the conveyor belt to the annealing lehr. More than 1,000 bulbs per minute can be produced on such a machine. Pressed Glassware Pressing is used for objects with a simple basic shape where the opening is wider than the base, this does not restrict surface decoration which may be complicated. A plunger is used to form the inner surface of the article by pushing the glass against the outer mould. Pressing can be hand-operated or fully automatic. SECONDARY GLASS PROCESSING Annealing Glass, like most other materials, contracts on cooling. However, due to its low thermal conductivity, it does not cool uniformly and the surfaces, which cool more rapidly, shrink more quickly than the centre. This produces uncontrolled strain in the article. If the internal surface of an unannealed container is scratched, the container will disintegrate. Badly annealed glass articles cannot withstand thermal shock and are liable to break in use. The excessive strain can be avoided by slow cooling at a controlled rate, called annealing. Annealing is done in an oven, called a lehr, through which glass articles pass on a slowly moving conveyor belt. A container, for example, would enter a lehr at approximately 450 oC. As the conveyor moves through the lehr, which is approximately 20m long, the temperature is at first increased to about 560 oC, at which the glass just begins to flow and is then gradually reduced to a temperature at which no further strain can be induced, and then cooled by fan air to room temperature. The time required for this process depends on the size of the article and the wall thickness but is normally completed in less than an hour. Toughening Glass has an extremely high compressive strength and therefore when it does so due to induced tension on the surface. Glass can be thermally strengthened by inducing invisible thin layers in compression on the outer surfaces. In order to break such toughened or tempered glass, the

compression has to be neutralized and additional tension applied. Toughened or tempered glass, the compression has to be neutralized and additional tension applied. Toughening is obtained by reheating the glass article uniformly to a temperature just above that at which deformation could take place and then rapidly cooling the surfaces by jets of air. If one can imagine a sheet of glass as consisting of 3 layers then the process becomes easier to understand. The air jets rapidly cool and freeze solid the outer layers while the inner layers continues to contract. While it is contracting it exerts compression on the outer layers while putting itself under tension. This method can be applied to flat glass or simple shapes like curved car windscreens or even tumblers. Glass thickness must be uniform, not too thin, and the shape of the article must be such that all surfaces can be uniformly cooled at the same time. Bottles do not satisfy these conditions and cannot be toughened in this way. However, it is possible to toughen bottles chemically by immersing hot bottles in a molten potassium salt. Potassium ions replace sodium ions on the surface and, being larger, create a very thin layer of compression. Toughened glass cannot be further processed since any damage to the surface will expose the centre layer, which is in tension, and the glass will shatter. The shattering of a car windscreen is a good example of this phenomenon. Coating The coating of glass surfaces has been practiced for centuries. Mirrors are a good example of this art. However, this method of giving glass new physical, chemical and optical properties has made great strides in the last few decades. Lightweight glass containers are coated with organic compounds to give the surfaces a degree of lubricity and thus preventing abrasion in handling. This adds strength to the container and has enabled glass manufacturers to make a lighter and better product. Coating containers with tin compounds also produces a stronger product. Coating glass containers with plastic materials for added strength and safety is a further way of lightweighting or increasing internal pressure resistance. Other forms of decorations are etching with hydrofluoric acid, sandblasting and vitreous enameling. In the latter, vitreous enamels, which are low melting point glasses held in an aqueous medium are deposited on the glass through very fine wire mesh screens and are then fired in an enameling furnace. The enamel thus becomes an integral part of the glass article. Decorating Formed and annealed glass may be further processed. This may be done by taking away from or adding to the surface of the glass. It may also be heated, manipulated, and reshaped. These methods include: 1. Taking away: A disturbance of the surface of glass may result in a matt or obscured finish. Where a transparent surface is then required this is produced by polishing on felt or wood wheels of by hydrofluoric acid solution. 2. Adding: Vitreous enamels, which are glasses that melt at relatively low temperature and can be colored, may be applied to the surface of formed glass. Metal compounds can also be applied. In both these cases the article is then reheated after application of the enamel or metal coating so that it fuses permanently to the surface of the glass. Also metal films can be applied by spraying, or by chemical or vapor deposition; and 3. Manipulating: Glass which has been formed and annealed may be reheated and manipulated into a new shape. It then has to be re-annealed and may be toughened.