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Dynamical heterogeneity describes the behavior of glass-forming materials when undergoing a phase transition from the liquid state to the glassy state. In dynamical heterogeneity, the dynamics of cooling to a glassy state show variation within the material.
Polymer properties include viscoelasticity and may be synthetic or natural. When a polymeric liquid is cooled below its freezing temperature without crystallizing, it becomes a supercooled liquid. When the supercooled liquid is further cooled, it becomes a glass. [1]
The temperature at which a polymer becomes a glass by fast cooling is called the glass transition temperature Tg. At this temperature, viscosity reaches up to 1013 poise depending upon cooling-rate.
It is possible for a phase transition from polymer to glassy state to take place. Polymer glass transitions have many determinants including relaxation time, viscosity and cage size. At low temperatures the dynamics become very slow (sluggish) and relaxation time increases from picoseconds to seconds, minutes, or more. At high temperatures, the correlation function has a ballistic regime for very short times (when particles do not interact) and a microscopic regime. In the microscopic regime, the correlation functions decay exponentially at high temperatures. At low temperatures the correlation functions have an intermediate regime in which particles have both slow and fast relaxations. The slow relaxation is an indication of cages in the glassy system. In glassy state density is not homogeneous i.e. particles are localized in different density distributions in space. It means that density fluctuations are present in the system. Particle dynamics become very slow because temperature is directly proportional to kinetic energy causing the particles trapped in local regions by each other. Particles are doing rattling motion inside these cages and cooperate with each other. These regions in the glassy polymer are called cages. In the intermediate regime each particle has its own and different relaxation time. [2]
The dynamics in all these cases are different, so at a small scale, there are a large number of cages in the system relative to the size of the whole system. This is known as dynamical heterogeneity in the glassy state of the system. A measurement of dynamical heterogeneity can be done by calculating correlation functions like Non-Gaussian parameter, four point correlation functions (Dynamic Susceptibility) and three time correlation functions. [3]
Melting, or fusion, is a physical process that results in the phase transition of a substance from a solid to a liquid. This occurs when the internal energy of the solid increases, typically by the application of heat or pressure, which increases the substance's temperature to the melting point. At the melting point, the ordering of ions or molecules in the solid breaks down to a less ordered state, and the solid melts to become a liquid.
Rheology is the study of the flow of matter, primarily in a liquid or gas state, but also as "soft solids" or solids under conditions in which they respond with plastic flow rather than deforming elastically in response to an applied force. Rheology is a branch of physics, and it is the science that deals with the deformation and flow of materials, both solids and liquids.
In chemistry, thermodynamics, and many other related fields, phase transitions are the physical processes of transition between the basic states of matter: solid, liquid, and gas, as well as plasma in rare cases.
Supercooling, also known as undercooling, is the process of lowering the temperature of a liquid or a gas below its freezing point without it becoming a solid. It achieves this in the absence of a seed crystal or nucleus around which a crystal structure can form. The supercooling of water can be achieved without any special techniques other than chemical demineralization, down to −48.3 °C (−55 °F). Droplets of supercooled water often exist in stratus and cumulus clouds. An aircraft flying through such a cloud sees an abrupt crystallization of these droplets, which can result in the formation of ice on the aircraft's wings or blockage of its instruments and probes.
An amorphous metal is a solid metallic material, usually an alloy, with disordered atomic-scale structure. Most metals are crystalline in their solid state, which means they have a highly ordered arrangement of atoms. Amorphous metals are non-crystalline, and have a glass-like structure. But unlike common glasses, such as window glass, which are typically electrical insulators, amorphous metals have good electrical conductivity and they also display superconductivity at low temperatures.
A lollipop is a type of sugar candy usually consisting of hard candy mounted on a stick and intended for sucking or licking. Different informal terms are used in different places, including lolly, sucker, sticky-pop, etc. Lollipops are available in many flavors and shapes.
In materials science, the sol–gel process is a method for producing solid materials from small molecules. The method is used for the fabrication of metal oxides, especially the oxides of silicon (Si) and titanium (Ti). The process involves conversion of monomers into a colloidal solution (sol) that acts as the precursor for an integrated network of either discrete particles or network polymers. Typical precursors are metal alkoxides.
Polyamorphism is the ability of a substance to exist in several different amorphous modifications. It is analogous to the polymorphism of crystalline materials. Many amorphous substances can exist with different amorphous characteristics. However, polyamorphism requires two distinct amorphous states with a clear, discontinuous (first-order) phase transition between them. When such a transition occurs between two stable liquid states, a polyamorphic transition may also be referred to as a liquid–liquid phase transition.
Thermomechanical analysis (TMA) is a technique used in thermal analysis, a branch of materials science which studies the properties of materials as they change with temperature.
The time–temperature superposition principle is a concept in polymer physics and in the physics of glass-forming liquids. This superposition principle is used to determine temperature-dependent mechanical properties of linear viscoelastic materials from known properties at a reference temperature. The elastic moduli of typical amorphous polymers increase with loading rate but decrease when the temperature is increased. Curves of the instantaneous modulus as a function of time do not change shape as the temperature is changed but appear only to shift left or right. This implies that a master curve at a given temperature can be used as the reference to predict curves at various temperatures by applying a shift operation. The time-temperature superposition principle of linear viscoelasticity is based on the above observation.
Jamming is the physical process by which the viscosity of some mesoscopic materials, such as granular materials, glasses, foams, polymers, emulsions, and other complex fluids, increases with increasing particle density. The jamming transition has been proposed as a new type of phase transition, with similarities to a glass transition but very different from the formation of crystalline solids.
The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water.
A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter, and is the only state with a definite volume but no fixed shape. A liquid is made up of tiny vibrating particles of matter, such as atoms, held together by intermolecular bonds. Like a gas, a liquid is able to flow and take the shape of a container. Most liquids resist compression, although others can be compressed. Unlike a gas, a liquid does not disperse to fill every space of a container, and maintains a fairly constant density. A distinctive property of the liquid state is surface tension, leading to wetting phenomena. Water is, by far, the most common liquid on Earth.
The glass–liquid transition, or glass transition, is the gradual and reversible transition in amorphous materials from a hard and relatively brittle "glassy" state into a viscous or rubbery state as the temperature is increased. An amorphous solid that exhibits a glass transition is called a glass. The reverse transition, achieved by supercooling a viscous liquid into the glass state, is called vitrification.
Johari-Goldstein relaxation, also known as the JG β-relaxation, is a universal property of glasses and certain other disordered materials. Proposed in 1969 by Martin Goldstein, JG β-relaxation were described as a secondary relaxation mechanism required to explain the viscosity behavior of liquids approaching the glass transition in the potential energy landscape picture presented in Goldstein's seminal 1969 paper. Previous experiments on glass forming liquids showed multiple relaxation times present in liquids measured by time dependent compliance measurements. Gyan P. Johari and Martin Goldstein measured the dielectric loss spectrum of a set of rigid glass forming molecules to further test the hypothesis of Goldstein in 1969. The relaxation, a peak in mechanical or dielectric loss at a particular frequency, had previously been attributed to a type of molecular flexibility [citation needed]. The fact that such a loss peak shows up in glasses of rigid molecules lacking this flexibility demonstrated its universal character. The JG β-relaxation process is speculated to be a precursor of the structural α-relaxation, i.e., its occurrence facilitates viscous flow, however the microscopic mechanism of the β-relaxation has not been definitively identified.
In condensed matter physics and physical chemistry, the terms viscous liquid, supercooled liquid, and glassforming liquid are often used interchangeably to designate liquids that are at the same time highly viscous, can be or are supercooled, and able to form a glass.
In glass physics, fragility characterizes how rapidly the dynamics of a material slow down as it is cooled toward the glass transition: materials with a higher fragility have a relatively narrow glass transition temperature range, while those with low fragility have a relatively broad glass transition temperature range. Physically, fragility may be related to the presence of dynamical heterogeneity in glasses, as well as to the breakdown of the usual Stokes–Einstein relationship between viscosity and diffusion.
Sharon C. Glotzer is an American scientist and "digital alchemist," the Anthony C. Lembke Department Chair of Chemical Engineering, the John Werner Cahn Distinguished University Professor of Engineering and the Stuart W. Churchill Collegiate Professor of Chemical Engineering at the University of Michigan, where she is also Professor of Materials Science & Engineering, Professor of Physics, Professor of Macromolecular Science & Engineering, and Professor of Applied Physics. She is recognized for her contributions to the fields of soft matter and computational science, most notably on problems in assembly science and engineering, nanoscience, and the glass transition, for which the elucidation of the nature of dynamical heterogeneity in glassy liquids is of particular significance. She is a member of the National Academy of Sciences, the National Academy of Engineering, and the American Academy of Arts and Sciences.
Cooperative segmental mobility is a phenomenon associated with mobility of tens to a few hundreds of repeat units of a polymer and is important in defining the transition between “glassy” and “rubbery” state of the polymer. This cooperative segmental mobility is closely related to the dynamics of the polymer near its glass transition temperature. In the glassy state, the relaxation process of a polymer chain is a cooperative phenomenon and the molecular motion depends to some degree on that of its neighbors.
Mechanics of gelation describes processes relevant to sol-gel process.
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