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Glass transition or vitrification refers to the transformation of a glass-forming liquid into a glass, which usually occurs upon rapid cooling. It is a dynamic phenomenon occurring between two distinct states of matter (liquid and glass), each with different physical properties. Upon cooling through the temperature range of glass transition (a "glass transformation range"), without forming any long-range order or significant symmetry of atomic arrangement, the liquid contracts more continuously at about the same rate as above the melting point until there is a decrease in the thermal expansion coefficient (TEC).[1]

The glass transition temperature, Tg, is lower than melting temperature, Tm, due to supercooling. It depends on the time scale of observation which must be defined by convention. One approach is to agree on a standard cooling rate of 10 K/min. Another approach is by requiring a viscosity of 1013 poise. Otherwise, one can only talk about a glass transformation range.

Glassblowing at temperatures just above the glass transition

Contents

Introduction

The glassy or vitreous state of matter is typically formed by rapid cooling and solidification from the molten (or liquid) state. If the liquid were allowed to crystallize on cooling, then according to the Ehrenfest classification of first-order phase transitions, there would be a discontinuous change in volume (and thus a discontinuity in the slope or first derivative with respect to temperature, dV/dT) at the melting point. In this context, glass and melt are distinct phases with an interfacial discontinuity having a surface of tension with a positive surface energy. Thus, a metastable parent phase is always stable with respect to the nucleation of small embryos or droplets from a daughter phase, provided it has a positive surface of tension. Such first-order transitions must proceed by the advancement of an interfacial region whose structure and properties vary discontinuously from the parent phase.[2][3][4][5]

Below the transition temperature range, the glassy structure does not relax in accordance with the cooling rate used. The expansion coefficient for the glassy state is roughly equivalent to that of the crystalline solid. If slower cooling rates are used, the increased time for structural relaxation (or intermolecular rearrangement) to occur may result in a higher density glass product. Similarly, by annealing (and thus allowing for slow structural relaxation) the glass structure in time approaches an equilibrium density corresponding to the supercooled liquid at this same temperature. Tg is located at the intersection between the cooling curve (volume versus temperature) for the glassy state and the supercooled liquid.[6][7][8][9][10]

The configuration of the glass in this temperature range changes slowly with time towards the equilibrium structure. The principle of the minimization of the Gibbs free energy provides the thermodynamic driving force necessary for the eventual change (see Physics of glass). It should be noted here that at somewhat higher temperatures than Tg, the structure corresponding to equilibrium at any temperature is achieved quite rapidly. In contrast, at considerably lower temperatures, the configuration of the glass remains sensibly stable over increasingly extended periods of time.

Thus, the liquid-glass transition is not a transition between states of thermodynamic equilibrium. It is widely believed that the true equilibrium state is always crystalline. Glass is believed to exist in a metastable state, and its entropy, density, and so on, depend on the thermal history. Therefore, the glass transition is primarily a dynamic phenomenon. Time and temperature are interchangeable quantities (to some extent) when dealing with glasses, a fact often expressed in the time-temperature superposition principle. On cooling a liquid, internal degrees of freedom successively fall out of equilibrium. However, there is a longstanding debate whether there is an underlying second-order phase transition in the hypothetical limit of infinitely long relaxation times.[11][12][13]

Transition temperature Tg

Measurement of Tg by differential scanning calorimetry
Determination of Tg by dilatometry.

Refer to the figure on the right plotting the heat capacity as a function of temperature. In this context, Tg is the temperature corresponding to point A on the curve. The linear sections below and above Tg are colored green. Tg is the temperature at the intersection of the red regression lines.[14]

Different operational definitions of the glass transition temperature Tg are in use, and several of them are endorsed as accepted scientific standards. Nevertheless, all definitions are arbitrary, and all yield different numeric results: at best, values of Tg for a given substance agree within a few kelvins. One definition refers to the viscosity, fixing Tg at a value of 1013 poise (or 1012 Pa·s). As evidenced experimentally, this value is close to the annealing point of many glasses.[15] The viscosity of amorphous materials is characterized in the glassy state by a high activation energy. Thermal fluctuations or lattice phonons break joining bonds. with higher temperatures resulting in higher concentrations of broken bonds (or configurons). According to Ojovan [16], at temperatures approaching Tg configurons begin to form large clusters which become macroscopically large above the Tg. Broken bonds facilitate the irreversible plastic deformation (or flow) of the glassy network. Also, the viscosity of amorphous materials is characterized in the liquid state by a low activation energy. The bond system of an amorphous material changes its Hausdorff-Besikovitch dimensionality from Euclidian 3 below Tg -- where the amorphous material responds mechanically as an elastic solid on most experimental timescales -- to fractal 2.55 (± 0.05) above Tg -- where the amorphous material exhibits the rheology observed in a classical liquid [17], [18].

In contrast to viscosity, the thermal expansion, heat capacity, and many other properties of inorganic glasses show a relatively sudden change at the glass transition temperature. Any such step or kink can be used to define Tg. To make this definition reproducible, the cooling or heating rate must be specified.

The most frequently used definition of Tg uses the energy release on heating in differential scanning calorimetry (DSC, see figure). Typically, the sample is first cooled with 10 K/min and then heated with that same speed.

Yet another definition of Tg uses the kink in dilatometry. Here, heating rates of 3-5 K/min are common. Summarized below are Tg values characteristic of certain classes of materials.

Material Tg (°C)
Tyre rubber −70[19]
Polypropylene (atactic) −20[20]
Poly(vinyl acetate) (PVAc) 30[20]
Polyethylene terephthalate (PET) 70[20]
Poly(vinyl alcohol) (PVA) 85[20]
Poly(vinyl chloride) (PVC) 80[20]
Polystyrene 95[20]
Polypropylene (isotactic) 0[20]
Poly-3-hydroxybutyrate (PHB) 15[20]
Poly(methylmethacrylate) (atactic) 105[20]
Poly(carbonate) 145[20]
Chalcogenide GeSbTe 150[21]
Chalcogenide AsGeSeTe 245
ZBLAN glass 235
Tellurium dioxide 280
Polynorbornene 215[20]
Fluoroaluminate 400
Soda-lime glass 520-600
Fused quartz ~1200[22]

These are only mean values, as the glass transition temperature depends on the cooling rate, molecular weight distribution and could be influenced by additives. Note also that for a semi-crystalline material, such as polyethylene that is 60-80% crystalline at room temperature, the quoted glass transition refers to what happens to the amorphous part of the material upon cooling.

Classes of materials

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Silica, SiO2

Tetrahedral structural unit of silica (SiO2), the basic building block of the most ideal glass former.

Ideal glass formers are typically composed of molecular networks whose intricate geometries do not lend themselves easily to long-range order formation and higher orders of symmetry. In the vast majority of silicates, the Si atom shows tetrahedral coordination, with 4 oxygen atoms surrounding a central Si atom.

All but one of the crystalline forms involve tetrahedral SiO4 units linked together by shared vertices in different arrangements. In different minerals the tetrahedra show different degrees of networking and polymerization. For example, they occur singly, joined together in pairs, in larger finite clusters including rings, in chains, double chains, sheets, and three-dimensional frameworks. The minerals are classified into groups based on these structures.

The most common example is seen in the quartz crystalline form of silicon dioxide, or silica SiO2. In each of the most thermodynamically stable crystalline forms of silica, on average, only 2 out of 4 of each the vertices (or oxygen atoms) of the SiO4 tetrahedra are shared with others, yielding the net chemical formula: SiO2. For example, in the unit cell of alpha-quartz, the central tetrahedron shares all 4 of its corner O atoms, the 2 face-centered tetrahedra share 2 of their corner O atoms, and the 4 edge-centered tetrahedra share just 1 of their O atoms with other SiO4 tetrahedra. This leaves a net average of 12 out of 24 (or 1 out of 2) total vertices for that portion of the 7 SiO4 tetrahedra which are considered to be a part of the unit cell for silica (see 3-D Unit Cell).[23]

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.

Silica (the chemical compound SiO2) has a number of distinct crystalline forms in addition to the quartz structure. Nearly all of the crystalline forms involve tetrahedral SiO4 units linked together by shared vertices in different arrangements. Si-O bond lengths vary between the different crystal forms. For example, in α-quartz the bond length is 161 pm, whereas in α-tridymite it ranges from 154-171 pm. The Si-O-Si bond angle also varies from 140° in α-tridymite to 144° in α-quartz to 180° in β-tridymite. Any deviations from these standard parameters constitute microstructural differences or variations which represent an approach to an amorphous, vitreous or glassy solid.

The transition temperature Tg in silicates is related to the energy required to break and re-form covalent bonds in an amorphous (or random network) lattice of covalent bonds. The Tg is clearly influenced by the chemistry of the glass. For example, addition of elements such as B, Na, K or Ca to a silica glass, which have a valency less than 4, helps in breaking up the network structure, thus reducing the Tg. Alternatively, P which has a valency of 5, helps to reinforce an ordered lattice, and thus increases the Tg.[24]

Fluorides

A bundle of optical fibers

Fluoride glass is a class of non-oxide optical quality glasses composed of fluorides of various metals. Due to their low viscosity, it is very difficult to completely avoid the occurrence of any crystallization while processing it through the glass transition (or drawing the fiber from the melt). Thus, although heavy metal fluoride glasses (HMFG) exhibit very low optical attenuation, they are not only difficult to manufacture, but are quite fragile, and have poor resistance to moisture and other environmental attacks. Their best attribute is that they lack the absorption band associated with the hydroxyl (OH) group (3200 - 3600 cm−1) which is present in nearly all oxide-based glasses.

An example of a heavy metal fluoride glass is the ZBLAN glass group, composed of zirconium, barium, lanthanum, aluminum, and sodium fluorides. Their main technological application is as optical waveguides in both planar and fibre form. They are advantageous especially in the mid-infrared (2 - 5 µm) range.

HMFG's were initially slated for optical fiber applications, because the intrinsic losses of a mid-IR fiber could in principle be lower than those of silica fibers, which are transparent only up to ~ 2 μm. However, such low losses were never realized in practice, and the fragility and high cost of fluoride fibers made them less than ideal as primary candidates. Later, the utility of fluoride fibers for various other applications was discovered. These include mid-IR spectroscopy, fiber-optic sensors, thermometry, and imaging. Also, fluoride fibers can be used to for guided lightwave transmission in media such as YAG (ytrria-alumina garnet) lasers at 2.9 μm, as required for medical applications (e.g. ophthalmology and dentistry).[25][26]

Phosphates

The P4O10 cagelike structure which provides the basic building block for phosphate glass formers.

Phosphate glass constitutes a class of optical glasses composed of metaphosphates of various metals. Instead of the SiO4 tetrahedra observed in silicate glasses, the building block for this glass former is P2O5, which crystallizes in at least four forms. The most familiar polymorph (see figure) comprises molecules of P4O10. The other polymorphs are polymeric, but in each case the phosphorus atoms are bound by a tetrahedron of oxygen atoms, one of which forms a terminal P=O bond. The O-form adopts a layered structure consisting of interconnected P6O6 rings, not unlike the structure adopted by certain polysilicates.

Iron phosphate and lead iron phosphate glass provide alternatives to borosilicate glass for the immobilization of radioactive waste. Phosphate glasses can also be advantageous over silica glasses for optical fibers with high concentration of doping rare earth ions. A mix of fluoride glass and phosphate glass is fluorophosphate glass.

Chalcogenides

The chalcogens — the elements in group VI of the periodic table, particularly sulphur (S), selenium (Se) and tellurium (Te) — react with more electropositive elements, such as silver, to form chalcogenides. These are extremly versatile compounds, in that they can be crystalline or amorphous, metallic or semiconducting, and conductors of ions or electrons. Already important in optical storage discs and fibers, they are now being proposed as the basis for solid-state memory technologies. Moreover, chalcogenide glass materials form the basis of CD and DVD technologies.

A compact disc (CD) utilizing chalcogenide glasses for solid-state memory technology.

Electrical switching in chalcogenide semiconductors emerged in the 1960s, when the amorphous chalcogenide Te48As30Si12Ge10 was found to exhibit sharp, reversible transitions in electrical resistance above a threshold voltage. The switching mechanism would appear initiated by fast purely electronic processes. If current is allowed to persist in the non-crystalline material, it heats up and changes to crystalline form. This is equivalent to information being written on it. A crystalline region may be melted by exposure to a brief, intense pulse of heat. Subsequent rapid cooling then sends the melted region back through the glass transition. Conversely, a lower-intensity heat pulse of longer duration will crystallize an amorphous region.

Attempts to induce the glassy–crystal transformation of chalcogenides by electrical means form the basis of phase-change random-access memory (PC-RAM). This emerging technology is on the brink of commercial application by ECD Ovonics. For write operations, an electric current supplies the heat pulse. The read process is performed at sub-threshold voltages by utilizing the relatively large difference in electrical resistance between the glassy and crystalline states. Examples of such phase change materials are GeSbTe and AgInSbTe. In optical discs, the phase change layer is usually sandwiched between dielectric layers of ZnS-SiO2. Other less common such materials are InSe, SbSe, SbTe, InSbSe, InSbTe, GeSbSe, GeSbTeSe, and AgInSbSeTe.

Although the electronic structural transitions relevant to both optical discs and PC-RAM were featured strongly, contributions from ions were not considered — even though amorphous chalcogenides can have significant ionic conductivities. At Euromat 2005, however, it was shown that ionic transport can also be useful for data storage in a solid chalcogenide electrolyte. At the nanoscale, this electrolyte consists of crystalline metallic islands of silver selenide (Ag2Se) dispersed in an amorphous semiconducting matrix of germanium selenide (Ge2Se3).

All of these technologies present exciting opportunities that are not restricted to memory, but include cognitive computing and reconfigurable logic circuits. It is too early to tell which technology will be selected for which applicaiotn. But scientific interest alone should drive the continuing research. For example, the migration of dissolved ions is required in the electrolytic case, but could limit the performance of a phase-change device. Diffusion of both electrons and ions participate in electromigration — widely studied as a degradation mechanism of the electrical conductors used in modern integrated circuits. Thus, a unified approach to the study of chalcogenides, assessing the collective roles of atoms, ions and electrons, may prove essential for both device performance and reliability.[27][28][29]

Amorphous metals

Samples of amorphous metal

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 becomes "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 titanium-based BMGs. Batches of amorphous steel have also been produced that demonstrate mechanical properties far exceeding those found in conventional steel alloys.[30][31][32][33]

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.[34][35]

Polymers

In polymers the glass transition temperature, Tg, is often expressed as the temperature at which the Gibbs free energy is such that the activation energy for the cooperative movement of 50 or so elements of the polymer is exceeded (reference required). This allows molecular chains to slide past each other when a force is applied. From this definition, we can see that the introduction of relatively stiff chemical groups (such as benzene rings) will interfere with the flowing process and hence increase Tg.

The stiffness of thermoplastics decreases due to this effect (see figure.) When the glass temperature has been reached, the stiffness stays the same for a while, i.e., at or near E2, until the temperature exceeds Tm, and the material melts. This region is called the rubber plateau.

In ironing, a fabric is heated through the glass-rubber transition.

In ironing, a fabric is heated through this transition so that the polymer chains become mobile. The weight of the iron then imposes a preferred orientation. Tg can be significantly decreased by addition of plasticizers into the polymer matrix. Smaller molecules of plasticizer embed themselves between the polymer chains, increasing the spacing and free volume, and allowing them to move past one another even at lower temperatures. The "new-car smell" is due to the initial outgassing of volatile small-molecule plasticizers used to modify interior plastics (e.g., dashboards) to keep them from cracking in the cold, winter weather. The addition of nonreactive side groups to a polymer can also make the chains stand off from one another, reducing Tg. If a plastic with some desirable properties has a Tg which is too high, it can sometimes be combined with another in a copolymer or composite material with a Tg below the temperature of intended use. Note that some plastics are used at high temperatures, e.g., in automobile engines, and others at low temperatures.

In viscoelastic materials, the presence of liquid-like behavior depends on the properties of and so varies with rate of applied load, i.e., how quickly a force is applied. The silicone toy 'Silly Putty' behaves quite differently depending on the time rate of applying a force: pull slowly and it flows, acting as a heavily viscous liquid; hit it with a hammer and it shatters, acting as a glass.

Stiffness versus temperature

On cooling, rubber undergoes a liquid-glass transition, which has also been called a rubber-glass transition. For example, the Space Shuttle Challenger disaster was caused by rubber O-rings that were being used well below their glass transition temperature on an unusually cold Florida morning, and thus could not flex adequately to form proper seals between sections of the two solid-fuel rocket boosters.

Biomaterials

When sucrose is cooled slowly, the result is crystal sugar (or rock candy), but, when cooled rapidly, the result can be in the form of syrupy cotton candy (candyfloss).

Vitrification can also occur when starting with a liquid such as water, usually through very rapid cooling or the introduction of agents that suppress the formation of ice crystals. Additives used in cryobiology or produced naturally by organisms living in polar regions are called cryoprotectants. Arctic frogs and some other ectotherms naturally produce glycerol or glucose in their livers to reduce ice formation. When glucose is used as a cryoprotectant by Arctic frogs, massive amounts of glucose are released at low temperature,[36] and a special form of insulin allows for this extra glucose to enter the cells. When the frog rewarms during spring, the extra glucose must be rapidly removed from the cells and recycled via renal excretion and storage in the bladder. Arctic insects also use sugars as cryoprotectants. Arctic fish use antifreeze proteins, sometimes appended with sugars, as cryoprotectant.

Vitrification technology is being used to cryopreserve cells, tissues and organs for transplantation. For years, glycerol has been used in cryobiology as a cryoprotectant for blood cells and bull sperm, allowing storage at liquid nitrogen temperatures. However, glycerol cannot be used to protect whole organs from damage. Instead, many biotechnology companies are currently researching the development of other cryoprotectants more suitable for such uses. A successful discovery may eventually make possible the bulk cryogenic storage (or "banking") of transplantable human and xenobiotic organs. A substantial step in that direction has already occurred. At the July 2005 annual conference of the Society for Cryobiology,[37] Twenty-First Century Medicine announced the vitrification of a rabbit kidney to -135°C with their proprietary vitrification cocktail. Upon rewarming, the kidney was successfully transplanted into a rabbit, with complete functionality and viability.

In the context of cryonics, especially in preservation of the human brain, vitrification of tissue is thought to be necessary to prevent destruction of the tissue or information encoded in the brain. At present, vitrification techniques have only been applied to brains (neurovitrification) by Alcor and to the upper body by the Cryonics Institute, but research is in progress by both organizations to apply vitrification to the whole body.

The scientific basis behind the cryonics is that proteins possess a glass transition temperature below which both anharmonic motions and long-range correlated motion within a single molecule are quenched. The origin of this transition is primarily due to "caging" by glassy water[38], but can also be modeled in the absence of explicit water molecules, suggesting that part of the transition is due to internal protein dynamics.[39]

Glass-ceramics

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 non-crystalline intergranular phase of grain boundaries. When applied to whiteware ceramics, vitreous means the material has an extremely low permeability to liquids, often but not always water, when determined by a specified test regime.

A high strength glass-ceramic cooktop with negligible thermal expansion.

The term mainly refers to a mix of lithium and aluminosilicates which 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 (TEC) of the crystalline ceramic phase can be balanced with the positive TEC of the glassy phase. At a certain point (~70% crystalline) the glass-ceramic has a net TEC near zero. This type of glass-ceramic exhibits excellent mechanical properties and can sustain repeated and quick temperature changes up to 1000 °C.

Vitrification may also occur naturally when lightning strikes the crystalline (e.g. quartz) grains found in most beach sand. In this case, the extreme and immediate heat of the lightning (~2500 °C) creates hollow, branching rootlike structures called fulgurite via fusion. Thus, fulgurite tubes have a glassy interior due to rapid cooling and solidification of the crystalline sand after the lightning strike. The size and length of the fulgurite depends on the strength of the lightning strike and the thickness of the sand bed. Many sand fulgurites average 1 or 2 inches (2.5 - 5 cm) in diameter and can be up to 30 inches (75 cm) long.

Colloidal glasses

Electron micrograph of surface of colloidal glass. Structure and morphology consist of short-range order with both interdomain and intradomain lattice defects.

A colloidal crystal is a highly ordered array of colloidal particles which can be formed over a very long range (from a few millimeters to one centimeter) in length, and which appear analogous to their atomic or molecular counterparts. One of the finest natural examples of this phenomenon can be found in precious opal, where brilliant regions of pure spectral color result from close-packed domains of colloidal spheres of amorphous silicon dioxide (or silica, SiO2).

Thus, it has been known for many years that, due to repulsive Coulombic interactions, electrically charged macromolecules in an aqueous environment can exhibit long-range crystal-like correlations with separation between the particles often being considerably greater than the individual particle diameter. Colloidal solids (both crystals and glasses) are receiving increased attention, largely due to their mechanisms of solidification and self-assembly, cooperative motion, structures similar to those observed in condensed matter (liquids, crystals and glasses) and structural phase transitions including the glass transition. Phase equilibrium has been considered within the context of their physical similarities (with appropriate scaling) to classical elastic solids. In contrast to atomic systems, however, the length or spatial scale is mesoscopic and determined by the spacing between the particles (the cube root of the particle concentration or vol% solids). Thus, colloidal crystals can also exhibit the microstructure of a glass-like amorphous solid on an appropriately larger spatial scale. Concentrated colloidal suspensions may exhibit a distinct glass transition as function of particle concentration or density.[40][41][42][43]

Kauzmann's paradox

Entropy difference between crystal and undercooled melt

As a liquid is supercooled, the difference in entropy between the liquid and solid phase decreases. By extrapolating the heat capacity of the supercooled liquid below its glass transition temperature, it is possible to calculate the temperature at which the difference in entropies becomes zero. This temperature has been named the Kauzmann temperature.

If a liquid could be supercooled below its Kauzmann temperature, and it did indeed display a lower entropy than the crystal phase, the consequences would be paradoxical. This Kauzmann paradox has been the subject of much debate and many publications since it was first put forward by Walter Kauzmann in 1948.[44]

One resolution of the Kauzmann paradox is to say that there must be a phase change before the entropy of the liquid decreases. In this scenario, the transition temperature is known as the calorimetric ideal glass transition temperature T0c. In this view, the glass transition is not merely a kinetic effect, i.e. merely the result of fast cooling of a melt, but there is an underlying thermodynamic basis for glass formation. The glass transition temperature:

Tg → T0c  as   dTdt → 0.

There are at least three other possible resolutions to the Kauzmann paradox. It could be that the heat capacity of the supercooled liquid near the Kauzmann temperature smoothly decreases to a smaller value. It could also be that a first order phase transition to another liquid state occurs before the Kauzmann temperature with the heat capacity of this new state being less than that obtained by extrapolation from higher temperature. Finally, Kauzmann himself resolved the entropy paradox by postulating that all supercooled liquids must crystallize before the Kauzmann temperature is reached.

See also

References

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  36. ^ Jack R. Layne, Jr., Richard E. Lee, Jr. (1995). "Adaptations of frogs to survive freezing" (PDF). Climate Research 5: 53–59. doi:10.3354/cr005053. http://www.int-res.com/articles/cr/5/c005p053.pdf. 
  37. ^ "Plenary Session: Fundamentals of Biopreservation". CRYO 2005 Scientific Program. Society for Cryobiology. July 24, 2005. http://www.me.umn.edu/events/cryo2005/program.html. Retrieved 2006-11-08. 
  38. ^ Vitkup D, Ringe D, Petsko GA, Karplus M (2001). "Solvent mobility and the protein 'glass' transition". Nature Structural Biology 7: 34–38. doi:10.1038/71231.  Entrez Pubmed 10625424
  39. ^ Salsbury FR, Han WG, Noodleman L, Brooks CL (2003). "Temperature-dependent behavior of protein-chromophore interactions: A theoretical study of a blue fluorescent antibody". Chemphyschem 4: 848–855. doi:10.1002/cphc.200300694.  Entrez Pubmed 12961983
  40. ^ Pusey, P.N. and van Megan, W., Phys. Rev. Lett., Vol. 59, p. 2083 (1987); Phys. Rev. A, Vol. 43, p. 5429 (1991)
  41. ^ van Megan, W., Underwood, S.M. and Pusey, P.N., Phys. Rev. Lett., Vol. 67, p. 1586 (1991)
  42. ^ van Megan, W. and Underwood, S.M., Phys. Rev. Lett, Vol. 70, p. 2766 (1993); Phys. Rev. E, Vol. 47, p. 248 (1993)
  43. ^ Lowen, H., Dynamics of Charged Colloidal Suspensions Across the Freezing and Glass Transition, in Ordering and Phase Transitions in Charged Colloids, Arora, A.k. and Tat, B.V.R., Eds. (VCH Publishers, New York, 1996)
  44. ^ Walter Kauzmann, The Nature of the Glassy State and the Behavior of Liquids at Low Temperatures; Chemical Reviews 43 (2), 1948.[1]

Further reading

  • Handbook of Glass Data ( Elsevier, 1993 )
  • Engineered Materials Handbook ( ASM International, 2005 )

External links


File:The Art of Blown
Glassblowing at temperatures just above the glass transition

Glass transition or vitrification refers to the transformation of a glass-forming liquid into a glass, which usually occurs upon rapid cooling. It is a dynamic phenomenon occurring between two distinct states of matter (liquid and glass), each with different physical properties. Upon cooling through the temperature range of glass transition (a "glass transformation range"), without forming any long-range order or significant symmetry of atomic arrangement, the liquid contracts more continuously at about the same rate as above the melting point until there is a decrease in the thermal expansion coefficient (TEC).[1]

The glass transition temperature, Tg, is lower than melting temperature, Tm, due to supercooling. It depends on the time scale of observation which must be defined by convention. One approach is to agree on a standard cooling rate of 10 K/min. Another approach is by requiring a viscosity of 1012 Pa·s. Otherwise, one can only talk about a glass transformation range.[2]

Contents

Introduction

The glassy or vitreous state of matter is typically formed by rapid cooling and solidification from the molten (or liquid) state. If the liquid were allowed to crystallize on cooling, then according to the Ehrenfest classification of first-order phase transitions, there would be a discontinuous change in volume (and thus a discontinuity in the slope or first derivative with respect to temperature, dV/dT) at the melting point. In this context, glass and melt are distinct phases with an interfacial discontinuity having a surface of tension with a positive surface energy. Thus, a metastable parent phase is always stable with respect to the nucleation of small embryos or droplets from a daughter phase, provided it has a positive surface of tension. Such first-order transitions must proceed by the advancement of an interfacial region whose structure and properties vary discontinuously from the parent phase.[3][4][5][6]

Below the transition temperature range, the glassy structure does not relax in accordance with the cooling rate used. The expansion coefficient for the glassy state is roughly equivalent to that of the crystalline solid. If slower cooling rates are used, the increased time for structural relaxation (or intermolecular rearrangement) to occur may result in a higher density glass product. Similarly, by annealing (and thus allowing for slow structural relaxation) the glass structure in time approaches an equilibrium density corresponding to the supercooled liquid at this same temperature. Tg is located at the intersection between the cooling curve (volume versus temperature) for the glassy state and the supercooled liquid.[7][8][9][10][11]

The configuration of the glass in this temperature range changes slowly with time towards the equilibrium structure. The principle of the minimization of the Gibbs free energy provides the thermodynamic driving force necessary for the eventual change (see Physics of glass). It should be noted here that at somewhat higher temperatures than Tg, the structure corresponding to equilibrium at any temperature is achieved quite rapidly. In contrast, at considerably lower temperatures, the configuration of the glass remains sensibly stable over increasingly extended periods of time.

Thus, the liquid-glass transition is not a transition between states of thermodynamic equilibrium. It is widely believed that the true equilibrium state is always crystalline. Glass is believed to exist in a kinetically locked state, and its entropy, density, and so on, depend on the thermal history. Therefore, the glass transition is primarily a dynamic phenomenon. Time and temperature are interchangeable quantities (to some extent) when dealing with glasses, a fact often expressed in the time-temperature superposition principle. On cooling a liquid, internal degrees of freedom successively fall out of equilibrium. However, there is a longstanding debate whether there is an underlying second-order phase transition in the hypothetical limit of infinitely long relaxation times.[12][13][14]

Transition temperature Tg

.]] Refer to the figure on the right plotting the heat capacity as a function of temperature. In this context, Tg is the temperature corresponding to point A on the curve. The linear sections below and above Tg are colored green. Tg is the temperature at the intersection of the red regression lines.[15]

Different operational definitions of the glass transition temperature Tg are in use, and several of them are endorsed as accepted scientific standards. Nevertheless, all definitions are arbitrary, and all yield different numeric results: at best, values of Tg for a given substance agree within a few kelvins. One definition refers to the viscosity, fixing Tg at a value of 1013 poise (or 1012 Pa·s). As evidenced experimentally, this value is close to the annealing point of many glasses.[16] The viscosity of amorphous materials is characterized in the glassy state by a high activation energy. Thermal fluctuations or lattice phonons break joining bonds. with higher temperatures resulting in higher concentrations of broken bonds (or configurons). According to Ojovan,[17] at temperatures approaching Tg configurons begin to form large clusters which become macroscopically large above the Tg. Broken bonds facilitate the irreversible plastic deformation (or flow) of the glassy network. Also, the viscosity of amorphous materials is characterized in the liquid state by a low activation energy. The bond system of an amorphous material changes its Hausdorff-Besikovitch dimensionality from Euclidian 3 below Tg -- where the amorphous material responds mechanically as an elastic solid on most experimental timescales—to fractal 2.55 (± 0.05) above Tg -- where the amorphous material exhibits the rheology observed in a classical liquid,.[18][19]

In contrast to viscosity, the thermal expansion, heat capacity, and many other properties of inorganic glasses show a relatively sudden change at the glass transition temperature. Any such step or kink can be used to define Tg. To make this definition reproducible, the cooling or heating rate must be specified.

The most frequently used definition of Tg uses the energy release on heating in differential scanning calorimetry (DSC, see figure). Typically, the sample is first cooled with 10 K/min and then heated with that same speed.

Yet another definition of Tg uses the kink in dilatometry. Here, heating rates of 3-5 K/min are common. Summarized below are Tg values characteristic of certain classes of materials.

MaterialTg (°C)
Tyre rubber−70[20]
Polypropylene (atactic)−20[21]
Poly(vinyl acetate) (PVAc)30[21]
Polyethylene terephthalate (PET)70[21]
Poly(vinyl alcohol) (PVA)85[21]
Poly(vinyl chloride) (PVC)80[21]
Polystyrene95[21]
Polypropylene (isotactic)0[21]
Poly-3-hydroxybutyrate (PHB)15[21]
Poly(methylmethacrylate) (atactic)105[21]
Poly(carbonate)145[21]
Chalcogenide GeSbTe150[22]
Chalcogenide AsGeSeTe245
ZBLAN glass235
Tellurium dioxide280
Polynorbornene215[21]
Fluoroaluminate400
Soda-lime glass520-600
Fused quartz~1200[23]

These are only mean values, as the glass transition temperature depends on the cooling rate, molecular weight distribution and could be influenced by additives. Note also that for a semi-crystalline material, such as polyethylene that is 60-80% crystalline at room temperature, the quoted glass transition refers to what happens to the amorphous part of the material upon cooling.

Classes of materials

Silica, SiO2

Ideal glass formers are typically composed of molecular networks whose intricate geometries do not lend themselves easily to long-range order formation and higher orders of symmetry. In the vast majority of silicates, the Si atom shows tetrahedral coordination, with 4 oxygen atoms surrounding a central Si atom.

All but one of the crystalline forms involve tetrahedral SiO4 units linked together by shared vertices in different arrangements. In different minerals the tetrahedra show different degrees of networking and polymerization. For example, they occur singly, joined together in pairs, in larger finite clusters including rings, in chains, double chains, sheets, and three-dimensional frameworks. The minerals are classified into groups based on these structures.

The most common example is seen in the quartz crystalline form of silicon dioxide, or silica SiO2. In each of the most thermodynamically stable crystalline forms of silica, on average, all 4 of the vertices (or oxygen atoms) of the SiO4 tetrahedra are shared with others, yielding the net chemical formula: SiO2 -(this can be understood as each O atom, being bonded to 2 Si atoms, contributes 1/2 to the stoichiometry). For example, in the unit cell of alpha-quartz, the central tetrahedron shares all 4 of its corner O atoms, the 2 face-centered tetrahedra share 2 of their corner O atoms, and the 4 edge-centered tetrahedra share just 1 of their O atoms with other SiO4 tetrahedra. This leaves a net average of 12 out of 24 (or 1 out of 2) total vertices for that portion of the 7 SiO4 tetrahedra which are considered to be a part of the unit cell for silica (see 3-D Unit Cell).[24]

(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.]]

Silica (the chemical compound SiO2) has a number of distinct crystalline forms in addition to the quartz structure. Nearly all of the crystalline forms involve tetrahedral SiO4 units linked together by shared vertices in different arrangements. Si-O bond lengths vary between the different crystal forms. For example, in α-quartz the bond length is 161 pm, whereas in α-tridymite it ranges from 154-171 pm. The Si-O-Si bond angle also varies from 140° in α-tridymite to 144° in α-quartz to 180° in β-tridymite. Any deviations from these standard parameters constitute microstructural differences or variations which represent an approach to an amorphous, vitreous or glassy solid.

The transition temperature Tg in silicates is related to the energy required to break and re-form covalent bonds in an amorphous (or random network) lattice of covalent bonds. The Tg is clearly influenced by the chemistry of the glass. For example, addition of elements such as B, Na, K or Ca to a silica glass, which have a valency less than 4, helps in breaking up the network structure, thus reducing the Tg. Alternatively, P which has a valency of 5, helps to reinforce an ordered lattice, and thus increases the Tg.[25]

Fluorides

s ]]

Fluoride glass is a class of non-oxide optical quality glasses composed of fluorides of various metals. Due to their low viscosity, it is very difficult to completely avoid the occurrence of any crystallization while processing it through the glass transition (or drawing the fiber from the melt). Thus, although heavy metal fluoride glasses (HMFG) exhibit very low optical attenuation, they are not only difficult to manufacture, but are quite fragile, and have poor resistance to moisture and other environmental attacks. Their best attribute is that they lack the absorption band associated with the hydroxyl (OH) group (3200 – 3600 cm−1) which is present in nearly all oxide-based glasses.

An example of a heavy metal fluoride glass is the ZBLAN glass group, composed of zirconium, barium, lanthanum, aluminum, and sodium fluorides. Their main technological application is as optical waveguides in both planar and fibre form. They are advantageous especially in the mid-infrared (2 - 5 µm) range.

HMFG's were initially slated for optical fiber applications, because the intrinsic losses of a mid-IR fiber could in principle be lower than those of silica fibers, which are transparent only up to ~ 2 μm. However, such low losses were never realized in practice, and the fragility and high cost of fluoride fibers made them less than ideal as primary candidates. Later, the utility of fluoride fibers for various other applications was discovered. These include mid-IR spectroscopy, fiber-optic sensors, thermometry, and imaging. Also, fluoride fibers can be used to for guided lightwave transmission in media such as YAG (ytrria-alumina garnet) lasers at 2.9 μm, as required for medical applications (e.g. ophthalmology and dentistry).[26][27]

Phosphates

Phosphate glass constitutes a class of optical glasses composed of metaphosphates of various metals. Instead of the SiO4 tetrahedra observed in silicate glasses, the building block for this glass former is P2O5, which crystallizes in at least four forms. The most familiar polymorph (see figure) comprises molecules of P4O10. The other polymorphs are polymeric, but in each case the phosphorus atoms are bound by a tetrahedron of oxygen atoms, one of which forms a terminal P=O bond. The O-form adopts a layered structure consisting of interconnected P6O6 rings, not unlike the structure adopted by certain polysilicates.[28]

Iron phosphate and lead iron phosphate glass provide alternatives to borosilicate glass for the immobilization of radioactive waste. Phosphate glasses can also be advantageous over silica glasses for optical fibers with high concentration of doping rare earth ions. A mix of fluoride glass and phosphate glass is fluorophosphate glass.[29]

Chalcogenides

The chalcogens — the elements in group VI of the periodic table, particularly sulphur (S), selenium (Se) and tellurium (Te) — react with more electropositive elements, such as silver, to form chalcogenides. These are extremely versatile compounds, in that they can be crystalline or amorphous, metallic or semiconducting, and conductors of ions or electrons. Already important in optical storage discs and fibers, they are now being proposed as the basis for solid-state memory technologies. Moreover, chalcogenide glass materials form the basis of CD and DVD technologies.

(CD) utilizing chalcogenide glasses for solid-state memory technology.]]

Electrical switching in chalcogenide semiconductors emerged in the 1960s, when the amorphous chalcogenide Te48As30Si12Ge10 was found to exhibit sharp, reversible transitions in electrical resistance above a threshold voltage. The switching mechanism would appear initiated by fast purely electronic processes. If current is allowed to persist in the non-crystalline material, it heats up and changes to crystalline form. This is equivalent to information being written on it. A crystalline region may be melted by exposure to a brief, intense pulse of heat. Subsequent rapid cooling then sends the melted region back through the glass transition. Conversely, a lower-intensity heat pulse of longer duration will crystallize an amorphous region.

Attempts to induce the glassy–crystal transformation of chalcogenides by electrical means form the basis of phase-change random-access memory (PC-RAM). This emerging technology is on the brink of commercial application by ECD Ovonics. For write operations, an electric current supplies the heat pulse. The read process is performed at sub-threshold voltages by utilizing the relatively large difference in electrical resistance between the glassy and crystalline states. Examples of such phase change materials are GeSbTe and AgInSbTe. In optical discs, the phase change layer is usually sandwiched between dielectric layers of ZnS-SiO2. Other less common such materials are InSe, SbSe, SbTe, InSbSe, InSbTe, GeSbSe, GeSbTeSe, and AgInSbSeTe.

Although the electronic structural transitions relevant to both optical discs and PC-RAM were featured strongly, contributions from ions were not considered — even though amorphous chalcogenides can have significant ionic conductivities. At Euromat 2005, however, it was shown that ionic transport can also be useful for data storage in a solid chalcogenide electrolyte. At the nanoscale, this electrolyte consists of crystalline metallic islands of silver selenide (Ag2Se) dispersed in an amorphous semiconducting matrix of germanium selenide (Ge2Se3).

All of these technologies present exciting opportunities that are not restricted to memory, but include cognitive computing and reconfigurable logic circuits. It is too early to tell which technology will be selected for which applicaiotn. But scientific interest alone should drive the continuing research. For example, the migration of dissolved ions is required in the electrolytic case, but could limit the performance of a phase-change device. Diffusion of both electrons and ions participate in electromigration — widely studied as a degradation mechanism of the electrical conductors used in modern integrated circuits. Thus, a unified approach to the study of chalcogenides, assessing the collective roles of atoms, ions and electrons, may prove essential for both device performance and reliability.[30][31][32]

Amorphous metals

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 becomes "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 titanium-based BMGs. Batches of amorphous steel have also been produced that demonstrate mechanical properties far exceeding those found in conventional steel alloys.[33][34][35][36]

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.[37][38]

Polymers

In polymers the glass transition temperature, Tg, is often expressed as the temperature at which the Gibbs free energy is such that the activation energy for the cooperative movement of 50 or so elements of the polymer is exceeded[citation needed]. This allows molecular chains to slide past each other when a force is applied. From this definition, we can see that the introduction of relatively stiff chemical groups (such as benzene rings) will interfere with the flowing process and hence increase Tg.[39]

The stiffness of thermoplastics decreases due to this effect (see figure.) When the glass temperature has been reached, the stiffness stays the same for a while, i.e., at or near E2, until the temperature exceeds Tm, and the material melts. This region is called the rubber plateau.

[[File:|thumb|right|In ironing, a fabric is heated through the glass-rubber transition.]]

In ironing, a fabric is heated through this transition so that the polymer chains become mobile. The weight of the iron then imposes a preferred orientation. Tg can be significantly decreased by addition of plasticizers into the polymer matrix. Smaller molecules of plasticizer embed themselves between the polymer chains, increasing the spacing and free volume, and allowing them to move past one another even at lower temperatures. The "new-car smell" is due to the initial outgassing of volatile small-molecule plasticizers used to modify interior plastics (e.g., dashboards) to keep them from cracking in the cold, winter weather. The addition of nonreactive side groups to a polymer can also make the chains stand off from one another, reducing Tg. If a plastic with some desirable properties has a Tg which is too high, it can sometimes be combined with another in a copolymer or composite material with a Tg below the temperature of intended use. Note that some plastics are used at high temperatures, e.g., in automobile engines, and others at low temperatures.[21]

In viscoelastic materials, the presence of liquid-like behavior depends on the properties of and so varies with rate of applied load, i.e., how quickly a force is applied. The silicone toy 'Silly Putty' behaves quite differently depending on the time rate of applying a force: pull slowly and it flows, acting as a heavily viscous liquid; hit it with a hammer and it shatters, acting as a glass.


On cooling, rubber undergoes a liquid-glass transition, which has also been called a rubber-glass transition. For example, the Space Shuttle Challenger disaster was caused by rubber O-rings that were being used well below their glass transition temperature on an unusually cold Florida morning, and thus could not flex adequately to form proper seals between sections of the two solid-fuel rocket boosters.

Biomaterials

When sucrose is cooled slowly, the result is crystal sugar (or rock candy), but, when cooled rapidly, the result can be in the form of syrupy cotton candy (candyfloss).

Vitrification can also occur when starting with a liquid such as water, usually through very rapid cooling or the introduction of agents that suppress the formation of ice crystals. Additives used in cryobiology or produced naturally by organisms living in polar regions are called cryoprotectants. Arctic frogs and some other ectotherms naturally produce glycerol or glucose in their livers to reduce ice formation. When glucose is used as a cryoprotectant by Arctic frogs, massive amounts of glucose are released at low temperature,[40] and a special form of insulin allows for this extra glucose to enter the cells. When the frog rewarms during spring, the extra glucose must be rapidly removed from the cells and recycled via renal excretion and storage in the bladder. Arctic insects also use sugars as cryoprotectants. Arctic fish use antifreeze proteins, sometimes appended with sugars, as cryoprotectant.

Vitrification technology is being used to cryopreserve cells, tissues and organs for transplantation. For years, glycerol has been used in cryobiology as a cryoprotectant for blood cells and bull sperm, allowing storage at liquid nitrogen temperatures. However, glycerol cannot be used to protect whole organs from damage. Instead, many biotechnology companies are currently researching the development of other cryoprotectants more suitable for such uses. A successful discovery may eventually make possible the bulk cryogenic storage (or "banking") of transplantable human and xenobiotic organs. A substantial step in that direction has already occurred. At the July 2005 annual conference of the Society for Cryobiology,[41] Twenty-First Century Medicine announced the vitrification of a rabbit kidney to -135°C with their proprietary vitrification cocktail. Upon rewarming, the kidney was successfully transplanted into a rabbit, with complete functionality and viability.

In the context of cryonics, especially in preservation of the human brain, vitrification of tissue is thought to be necessary to prevent destruction of the tissue or information encoded in the brain. At present, vitrification techniques have only been applied to brains (neurovitrification) by Alcor and to the upper body by the Cryonics Institute, but research is in progress by both organizations to apply vitrification to the whole body.

The scientific basis behind the cryonics is that proteins possess a glass transition temperature below which both anharmonic motions and long-range correlated motion within a single molecule are quenched. The origin of this transition is primarily due to "caging" by glassy water,[42] but can also be modeled in the absence of explicit water molecules, suggesting that part of the transition is due to internal protein dynamics.[43]

Glass-ceramics

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 non-crystalline intergranular phase of grain boundaries. When applied to whiteware ceramics, vitreous means the material has an extremely low permeability to liquids, often but not always water, when determined by a specified test regime.[1][2]

.]]

The term mainly refers to a mix of lithium and aluminosilicates which 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 (TEC) of the crystalline ceramic phase can be balanced with the positive TEC of the glassy phase. At a certain point (~70% crystalline) the glass-ceramic has a net TEC near zero. This type of glass-ceramic exhibits excellent mechanical properties and can sustain repeated and quick temperature changes up to 1000 °C.[1][2]

Vitrification may also occur naturally when lightning strikes the crystalline (e.g. quartz) grains found in most beach sand. In this case, the extreme and immediate heat of the lightning (~2500 °C) creates hollow, branching rootlike structures called fulgurite via fusion. Thus, fulgurite tubes have a glassy interior due to rapid cooling and solidification of the crystalline sand after the lightning strike. The size and length of the fulgurite depends on the strength of the lightning strike and the thickness of the sand bed. Many sand fulgurites average 1 or 2 inches (2.5 – 5 cm) in diameter and can be up to 30 inches (75 cm) long.

Colloidal glasses

A colloidal crystal is a highly ordered array of colloidal particles which can be formed over a very long range (from a few millimeters to one centimeter) in length, and which appear analogous to their atomic or molecular counterparts. One of the finest natural examples of this phenomenon can be found in precious opal, where brilliant regions of pure spectral color result from close-packed domains of colloidal spheres of amorphous silicon dioxide (or silica, SiO2).

Because of repulsive Coulombic interactions, electrically charged macromolecules in an aqueous environment can exhibit long-range crystal-like correlations with separation between the particles often being considerably greater than the individual particle diameter. Colloidal solids (both crystals and glasses) are receiving increased attention, largely due to their mechanisms of solidification and self-assembly, cooperative motion, structures similar to those observed in condensed matter (liquids, crystals and glasses) and structural phase transitions including the glass transition. Phase equilibrium has been considered within the context of their physical similarities (with appropriate scaling) to classical elastic solids. In contrast to atomic systems, however, the length or spatial scale is mesoscopic and determined by the spacing between the particles (the cube root of the particle concentration or vol% solids). Thus, colloidal crystals can also exhibit the microstructure of a glass-like amorphous solid on an appropriately larger spatial scale. Concentrated colloidal suspensions may exhibit a distinct glass transition as function of particle concentration or density.[44][45][46][47]

Kauzmann's paradox

As a liquid is supercooled, the difference in entropy between the liquid and solid phase decreases. By extrapolating the heat capacity of the supercooled liquid below its glass transition temperature, it is possible to calculate the temperature at which the difference in entropies becomes zero. This temperature has been named the Kauzmann temperature.

If a liquid could be supercooled below its Kauzmann temperature, and it did indeed display a lower entropy than the crystal phase, the consequences would be paradoxical. This Kauzmann paradox has been the subject of much debate and many publications since it was first put forward by Walter Kauzmann in 1948.[48]

One resolution of the Kauzmann paradox is to say that there must be a phase change before the entropy of the liquid decreases. In this scenario, the transition temperature is known as the calorimetric ideal glass transition temperature T0c. In this view, the glass transition is not merely a kinetic effect, i.e. merely the result of fast cooling of a melt, but there is an underlying thermodynamic basis for glass formation. The glass transition temperature:

Tg → T0c  as   dTdt → 0.

There are at least three other possible resolutions to the Kauzmann paradox. It could be that the heat capacity of the supercooled liquid near the Kauzmann temperature smoothly decreases to a smaller value. It could also be that a first order phase transition to another liquid state occurs before the Kauzmann temperature with the heat capacity of this new state being less than that obtained by extrapolation from higher temperature. Finally, Kauzmann himself resolved the entropy paradox by postulating that all supercooled liquids must crystallize before the Kauzmann temperature is reached.

See also

References

  1. ^ a b c Kingery, W,D., Bowen, H.K., and Uhlmann, D.R., Introduction to Ceramics, 2nd Edn. (John Wiley & Sons, New York, 2006)
  2. ^ a b c Richerson, D.W., Modern Ceramic Engineering,2nd Ed., (Marcel Dekker Inc., 1992) ISBN 0-8247-8634-3.
  3. ^ Atkins, P.W., Physical Chemistry (W.H. Freeman & Co., New York, 1994)
  4. ^ Hilliard, J.E. and Cahn, J.W., On the Nature of the Interface Between a Solid Metal and Its Melt, Acta Met., Vol. 6, p. 772 (1958)
  5. ^ Cahn, J.W., Theory of crystal growth and interface motion in crystalline materials, Acta Met, Vol. 8, p. 554 (1960)
  6. ^ Cahn, J.W., Hillig, W.B. and Sears, G.W., The molecular mechanism of solidification, Acta Met., Vol. 12, p. 1421 (1964)
  7. ^ Moynihan, C. et al. in The Glass Transition and the Nature of the Glassy State, Eds. M. Goldstein and R. Simha, Ann. N.Y. Acad. Sci., Vol. 279 (1976)
  8. ^ Angell, C.A., J. Phys. Chem. Solids, Vol. 49, p. 863 (1988)
  9. ^ Angell, C.A. and Nagel, S.R., J. Phys. Chem., Vol. 100, p. 13200 (1996)
  10. ^ Angell, C.A., Science, Vol. 267, p. 1924 (1995)
  11. ^ Stillinger, F., Science, Vol. 267, p. 1935 (1995)
  12. ^ Nemilov, S.V., (1994). Thermodynamic and Kinetic Aspects of the Vitreous State. CRC Press. 
  13. ^ Zarzycki, J. (1991). Glasses and the Vitreous State. Cambridge University Press. 
  14. ^ J.H. Gibbs (1960). J.D. MacKenzie. ed. Modern Aspects of the Vitreous State. Butterworth. OCLC 1690554. 
  15. ^ Tg measurement of glasses
  16. ^ IUPAC Compendium of Chemical Terminology, 66, 583 (1984), http://old.iupac.org/goldbook/G02641.pdf
  17. ^ Ojovan, M.I., Viscosity and Glass Transition in Amorphous Oxides, Advances in Condensed Matter Physics, 2008, Article ID 817829, 23 pages (2008). http://www.hindawi.com/GetArticle.aspx?doi=10.1155/2008/817829
  18. ^ M.I. Ojovan, W.E. Lee., Topologically disordered systems at the glass transition, J. Phys.: Condensed Matter, Vol. 18, p. 11507 (2006)
  19. ^ Ojovan, M.I., Configurons: thermodynamic parameters and symmetry changes at the glass transition, Entropy, Vol. 10, p. 334 (2008)
  20. ^ [Expression error: Unexpected < operator Tyre comprising a cycloolefin polymer, tread band and elasomeric composition used therein]. 03.07.2003. 
  21. ^ a b c d e f g h i j k l Charles E. Wilkes, James W. Summers, Charles Anthony Daniels, Mark T. Berard (2005). PVC Handbook. Hanser Verlag. ISBN 1569903794. http://books.google.com/?id=YUkJNI9QYsUC&pg=PT1&lpg=PT1. 
  22. ^ EPCOS 2007: Glass Transition and Crystallization in Phase Change Materials
  23. ^ Bucaro, J. A. (1974). [Expression error: Unexpected < operator "High-temperature Brillouin scattering in fused quartz"]. Journal of Applied Physics 45: 5324–1974. doi:10.1063/1.1663238.  edit
  24. ^ Kihara, K., An X-ray study of the temperature dependence of the quartz structure, European Journal of Mineralogy, Vol. 2, p. 63 (1990)
  25. ^ Ojovan M.I. (2008). "Configurons: thermodynamic parameters and symmetry changes at glass transition". Entropy 10: 334–364. doi:10.3390/e10030334. http://www.mdpi.org/entropy/papers/e10030334.pdf. 
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Further reading

  • Handbook of Glass Data ( Elsevier, 1993 )
  • Engineered Materials Handbook ( ASM International, 2005 )

External links


Simple English

Above a glass transition temperature (Tm), a plastic is rubbery. Below the glass transition temperature, a plastic is solid.

Thermosets burn up before they reach their glass transition temperature.


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