Flory–Fox equation
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In polymer chemistry and polymer physics, the Flory–Fox equation is a simple empirical formula that relates molecular weight to the glass transition temperature of a polymer system. The equation was first proposed in 1950 by Paul J. Flory and Thomas G. Fox while at Cornell University.[1] Their work on the subject overturned the previously held theory that the glass transition temperature was the temperature at which viscosity reached a maximum. Instead, they demonstrated that the glass transition temperature is the temperature at which the free space available for molecular motions achieved a minimum value.[2] While its accuracy is usually limited to samples of narrow range molecular weight distributions, it serves as a good starting point for more complex structure-property relationships.
Recent molecular simulations have demonstrated that while the functional form of the Flory-Fox relation holds for a wide range of molecular architectures (linear chain, bottlebrush, star, and ring polymers), however, the central free-volume argument of the Flory-Fox relation does not hold since branched polymers, despite having more free ends, form materials of higher density and glass transition temperature increases.[3] [4]