Glass Glass generally refers to hard, brittle, transparent material, such as those used for windows, many bottles, or eyewear. Examples of such solid materials include, but are not limited to, soda-lime glass, borosilicate glass, acrylic glass, sugar glass, Muscovy-glass, or aluminium oxynitride. In the technical sense, glass is an inorganic product of fusion which has been cooled through the glass transition to a rigid condition without crystallizing. Many glasses contain silica as their main component and glass former. In the scientific sense the term glass is often extended to all amorphous solids (and melts that easily form amorphous solids), including plastics, resins, or other silica-free amorphous solids. In addition, besides traditional melting techniques, any other means of preparation are considered, such as ion implantation, and the sol-gel method. However, glass science and physics commonly includes only inorganic amorphous solids, while plastics and similar organics are covered by polymer science, biology and further scientific disciplines. Glass plays an essential role in science and industry. The optical and physical properties of glass make it suitable for applications such as flat glass, container glass, optics and optoelectronics material, laboratory equipment, thermal insulator (glass wool), reinforcement fiber (glass-reinforced plastic, glass fiber reinforced concrete), and art. The term glass developed in the late Roman Empire. It was in the Roman glassmaking center at Trier, Germany, that the late-Latin term glesum originated, probably from a Germanic word for a transparent, lustrous substance. Glass production As well as soda and lime, most common glass has other ingredients added to change its properties. Lead glass, such as lead crystal or flint glass, is more 'brilliant' because the increased refractive index causes noticeably more "sparkles", while boron may be added to change the thermal and electrical properties, as in Pyrex. 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index and low dispersion, and was formerly used in producing high-quality lenses, but due to its radioactivity has been replaced by lanthanum oxide in modern eye glasses. Large amounts of iron are used in glass that absorbs infrared energy, such as heat absorbing filters for movie projectors, while cerium(IV) oxide can be used for glass that absorbs UV wavelengths (biologically damaging ionizing radiation). Two other common glass ingredients are calumite (an iron industry by-product) and "cullet" (recycled glass). The recycled glass saves on raw materials and energy. However, impurities in the cullet can lead to product and equipment failure. Finally, fining agents such as sodium sulfate, sodium chloride, or antimony oxide are added to reduce the bubble content in the glass. Glass batch calculation is the method by which the correct raw material mixture is determined to achieve the desired glass composition. Contemporary glass production 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). Glassmaking in the laboratory 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 (the melt is cooled whilst floating in a gas stream), splat quenching, (the melt is pressed between two metal anvils) and roller quenching (the melt is poured through rollers). Sol-gel science/technology Silica-free glasses Some glasses that do not include silica as a major constituent may have physico-chemical properties useful for their application in fibre optics and other specialized technical applications. These include fluoride glasses (fluorozirconates, fluoroaluminates), aluminosilicates, phosphate glasses and chalcogenide glasses. Under extremes of pressure and temperature solids may exhibit large structural and physical changes which 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(a-CO2) and exhibits an atomic structure resembling that of Silica. Physics of glass The amorphous structure of glassy Silica (SiO2). No long range order is present, however there is local ordering with respect to the tetrahedral arrangement of Oxygen (O) atoms around the Silicon (Si) atoms. The standard definition of a glass (or vitreous solid) is a solid formed by rapid melt quenching. 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 the glass transition temperature 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. 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. It is deemed that the bonding structure of glasses, although disordered, has the same symmetry signature (Hausdorff-Besicovitch dimensionality) as for crystalline materials. Glass is generally classed as an amorphous solid rather than a liquid. Glass 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). From a more commonsense point of view, glass should be considered a solid since it is rigid according to everyday experience. 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 continuous through the glass transition range. However, the glass transition may be described as analogous to a second-order 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 in solids does not entirely hold for glass, and hence the glass transition cannot be classed as one of the classical equilibrium phase transformations in solids. 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 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 translational motion is arrested. This helps to explain why both crystalline and non-crystalline solids exhibit rigidity on most experimental time scales. Behavior of antique glass 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. Modern glass intended for windows is produced as float glass and is very uniform in thickness. Several other points exemplify the misconception of the "cathedral glass" theory: * Writing in the American Journal of Physics, physicist 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 much longer than the estimated age of the Universe.) Some glasses have a glass transition temperature close to or below room temperature. The behavior of a material that has a glass transition close to room temperature depends upon the timescale during which the material is manipulated. If the material is hit it may break like a solid glass, but if the material is left on a table for a week it may flow like a liquid. This simply means that for the fast timescale its transition temperature is above room temperature, but for the slow one it is below. The shift in temperature with timescale is not very large however, as indicated by the transition of polypropylene glycol of -72 °C and -71 °C over different timescales. To observe window glass flowing as liquid at room temperature we would have to wait a much longer time than any human can exist. Therefore it is safe to consider a glass a solid far enough below its transition temperature: Cathedral glass does not flow because its glass transition temperature is many hundreds of degrees above room temperature. Close to this temperature there are interesting time-dependent properties. One of these is known as aging. Many polymers that we use in daily life such as polystyrene and polypropylene are in a glassy state but they are not too far below their glass transition temperature as opposed to rubber which is used above its glass transition temperature. Their mechanical properties may well change over time and this is serious concern when applying these materials in construction. In general for polymers there is a relation between the glass transition temperature and the speed of the deformation. Physical properties Color Thus, 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, although iron(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. Manganese dioxide can be added in small amounts to remove the green tint given by iron(II) oxide. Optical waveguides An optical fiber is a cylindrical dielectric waveguide that transmits light along its axis by the process of total internal reflection. The fiber consists of a core surrounded by a cladding layer. To confine the optical signal in the core, the refractive index of the core must be greater than that of the cladding. The index of refraction is a way of measuring the speed of light in a material. (Note: The index of refraction is the ratio of the speed of light in a vacuum to the speed of light in a given medium. (The index of refraction of a vacuum is therefore equal to 1, by definition). The larger the index of refraction, the more slowly light travels in that medium. Typical values for core and cladding of an optical fiber are 1.48 and 1.46, respectively. When light traveling in a dense medium hits a boundary at a steep angle, the light will be completely reflected. This effect is used in optical fibers to confine light in the core. Light travels along the fiber bouncing back and forth off of the boundary. Because the light must strike the boundary with an angle greater than the critical angle, only light that enters the fiber within a certain range of angles will be propagated. This range of angles is called the acceptance cone of the fiber. The size of this acceptance cone is a function of the refractive index difference between the fiber's core and cladding. Optical waveguides are used as components in integrated optical circuits (e.g. light-emitting diodes, LEDs) or as the transmission medium in local and long haul optical communication systems. Also of value to the emerging materials scientist is the sensitivity of materials to thermal radiation in the infrared (IR) portion of the EM spectrum. This infrared homing (or "heat-seeking") capability is responsible for such diverse optical phenomena as "night vision" and IR luminescence. History During the Late Bronze Age in Egypt and Western Asia there was an explosion in glass-making technology. Archaeological finds from this period include colored glass ingots, vessels (often colored and shaped in imitation of highly prized wares of semi-precious stones) and the ubiquitous beads. The alkali of Syrian and Egyptian glass was soda ash, sodium carbonate, which can be extracted from the ashes of many plants, notably halophile seashore plants: (see saltwort). The earliest vessels were 'core-wound', produced by winding a ductile rope of glass round a shaped core of sand and clay over a metal rod, then fusing it with repeated reheatings. Threads of thin glass of different colors made with admixtures of oxides were subsequently wound around these to create patterns, which could be drawn into festoons by using metal raking tools. The vessel would then be rolled flat ('marvered') on a slab in order to press the decorative threads into its body. Handles and feet were applied separately. The rod was subsequently allowed to cool as the glass slowly annealed and was eventually removed from the center of the vessel, after which the core material was scraped out. Glass shapes for inlays were also often created in moulds. Much early glass production, however, relied on grinding techniques borrowed from stone working. This meant that the glass was ground and carved in a cold state. By the 15th century BC extensive glass production was occurring in Western Asia and Egypt. It is thought the techniques and recipes required for the initial fusing of glass from raw materials was a closely guarded technological secret reserved for the large palace industries of powerful states. Glass workers in other areas therefore relied on imports of pre-formed glass, often in the form of cast ingots such as those found on the Ulu Burun shipwreck off the coast of Turkey. Glass remained a luxury material, and the disasters that overtook Late Bronze Age civilisations seem to have brought glass-making to a halt. It picked up again in its former sites, in Syria and Cyprus, in the ninth century BC, when the techniques for making colorless glass were discovered. The first glassmaking "manual" dates back to ca. 650 BC. Instructions on how to make glass are contained in cuneiform tablets discovered in the library of the Assyrian king Ashurbanipal. In Egypt glass-making did not revive until it was reintroduced in Ptolemaic Alexandria. Core-formed vessels and beads were still widely produced, but other techniques came to the fore with experimentation and technological advancements. During the Hellenistic period many new techniques of glass production were introduced and glass began to be used to make larger pieces, notably table wares. Techniques developed during this period include 'slumping' viscous (but not fully molten) glass over a mould in order to form a dish and 'millefiori' (meaning 'thousand flowers') technique, where canes of multi-colored glass were sliced and the slices arranged together and fused in a mould to create a mosaic-like effect. It was also during this period that colorless or decolored glass began to be prized and methods for achieving this effect were investigated more fully. According to Pliny the Elder, Phoenician traders were the first to stumble upon glass manufacturing techniques at the site of the Belus River. Georgius Agricola, in De re metallica, reported a traditional serendipitous "discovery" tale of familiar type: "The tradition is that a merchant ship laden with nitrum being moored at this place, the merchants were preparing their meal on the beach, and not having stones to prop up their pots, they used lumps of nitrum from the ship, which fused and mixed with the sands of the shore, and there flowed streams of a new translucent liquid, and thus was the origin of glass." This account is more a reflection of Roman experience of glass production, however, as white silica sand from this area was used in the production of Roman glass due to its low impurity levels. During the first century BC glass blowing was discovered on the Syro-Palestinian coast, revolutionising the industry and laying the way for the explosion of glass production that occurred throughout the Roman world. It was the Romans who began to use glass for architectural purposes, with the discovery of clear glass (through the introduction of manganese oxide), in Alexandria ca. AD 100. Cast glass windows, albeit with poor optical qualities, thus began to appear in the most important buildings in Rome and the most luxurious villas of Herculaneum and Pompeii. Over the next 1,000 years glass making and working continued and spread through southern Europe and beyond. South Asia Chalcolithic evidence of glass has been found in Hastinapur, India. Some of the texts which mention glass in India are the Shatapatha Brahmana and Vinaya Pitaka. However, the first unmistakable evidence in large quantities, dating from the 3rd century BCE, has been uncovered from the archaeological site in Taxila, Pakistan. By the first century C.E., glass was being used for ornaments and casing in South Asia. Contact with the Greco-Roman world added newer techniques, and Indians artisans mastered several techniques of glass molding, decorating and coloring by the succeeding centuries. The Satavahana period of India also produced short cylinders of composite glass, including those displaying a lemon yellow matrix covered with green glass. Romans Anglo-Saxon world Islamic world The Arab poet al-Buhturi (820–897) described the clarity of such glass, "Its color hides the glass as if it is standing in it without a container." Stained glass was also first produced by Muslim architects in Southwest Asia using colored glass rather than stone. In the 8th century, the Arab chemist Jabir ibn Hayyan (Geber) scientifically described 46 original recipes for producing colored glass in Kitab al-Durra al-Maknuna (The Book of the Hidden Pearl), in addition to 12 recipes inserted by al-Marrakishi in a later edition of the book. The parabolic mirror was first described by Ibn Sahl in his On the Burning Instruments in the 10th century, and later described again in Ibn al-Haytham's On Burning Mirrors and Book of Optics (1021). By the 11th century, clear glass mirrors were being produced in Islamic Spain. The first glass factories were also built by Muslim craftsmen in the Islamic world. The first glass factories in Christian Europe were later built in the 11th century by Muslim Egyptian craftsmen in Corinth, Greece. Medieval Europe Until the 12th century, stained glass – glass to which metallic or other impurities had been added for coloring – was not widely used. The 11th century saw the emergence in Germany of new ways of making sheet glass by blowing spheres. The spheres were swung out to form cylinders and then cut while still hot, after which the sheets were flattened. This technique was perfected in 13th century Venice. The Crown glass process was used up to the mid-19th century. In this process, the glassblower would spin approximately 9 pounds (4 kg) of molten glass at the end of a rod until it flattened into a disk approximately 5 feet (1.5 m) in diameter. The disk would then be cut into panes. Late medieval Northern Europe Murano glassmaking The Venetian ability to produce this superior form of glass resulted in a trade advantage over other glass producing lands. Murano’s reputation as a center for glassmaking was born when the Venetian Republic, fearing fire might burn down the city’s mostly wood buildings, ordered glassmakers to move their foundries to Murano in 1291. Murano's glassmakers were soon the island’s most prominent citizens. Glassmakers were not allowed to leave the Republic. Many took a risk and set up glass furnaces in surrounding cities and as far afield as England and the Netherlands. Glass art Several of the most common techniques for producing glass art include: blowing, kiln-casting, fusing, slumping, pate-de-verre, flame-working, hot-sculpting and cold-working. Cold work includes traditional stained glass work as well as other methods of shaping glass at room temperature. Glass can also be cut with a diamond saw, or copper wheels embedded with abrasives, and polished to give gleaming facets; the technique used in creating Waterford crystal. Art is sometimes etched into glass via the use of acid, caustic, or abrasive substances. Traditionally this was done after the glass was blown or cast. In the 1920s a new mould-etch process was invented, in which art was etched directly into the mould, so that each cast piece emerged from the mould with the image already on the surface of the glass. This reduced manufacturing costs and, combined with a wider use of colored glass, led to cheap glassware in the 1930s, which later became known as Depression glass. As the types of acids used in this process are extremely hazardous, abrasive methods have gained popularity. Objects made out of glass include not only traditional objects such as vessels (bowls, vases, bottles, and other containers), paperweights, marbles, beads, but an endless range of sculpture and installation art as well. Colored glass is often used, though sometimes the glass is painted, innumerable examples exist of the use of stained glass. The Harvard Museum of Natural History has a collection of extremely detailed models of flowers made of painted glass. These were lampworked by Leopold Blaschka and his son Rudolph, who never revealed the method he used to make them. The Blaschka Glass Flowers are still an inspiration to glassblowers today. Web References: |
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