Illustrated Physics
physics, drawn
Concept

Glass transition — where it appears

The temperature at which a cooling liquid stops being able to rearrange itself within the time available, so that it keeps whatever structure and entropy it had. It moves down by three to five kelvin for every factor of ten in cooling rate, which is why a glass's properties are a property of its history.

Named by 3 essays across 2 fields — each of them below, with the objects they name alongside it.

One word, two mechanisms, opposite signs. Viscosity on a logarithmic axis against temperature over the range 280 to 360 kelvin, where gases and liquids can both be measured. The gases rise and the liquids fall, and the two families are separated by three decades of magnitude as well as by sign. The logarithmic slopes at the middle of the range are 0.76 for air, 0.69 for helium, -6.13 for water, -5.41 for ethanol, -23.00 for glycerol, so the steepest liquid responds 30 times more strongly than the gas and in the other direction. Nothing about the word viscosity requires this: what is being measured in both cases is the ratio of a shear stress to a shear rate, and that definition says nothing about what carries the momentum. In a gas it is molecules in free flight, so heating speeds up the carriers; in a liquid the molecules are permanently in contact and what has to happen is one of them getting past its neighbours, so heating removes an obstacle rather than adding a carrier. The obvious question this raises is what a dense gas near its critical point does, where neither picture holds, and the honest answer is that neither formula on this chart applies there at all.

The thickness that goes both ways

Heat a liquid and it thins; heat a gas and it thickens. The two are not a strong effect and a weak one but opposite signs, differing by a factor of thirty in size as well — and the word viscosity names one measurement made on two mechanisms that have almost nothing in common.

fluids · Viscosity The entropy a substance keeps depends on how fast it was cooled. The entropy of a supercooled liquid in excess of its crystal's, against temperature, for a substance melting at 305 K with an entropy of fusion of 43 joules per kelvin per mole and a liquid heat capacity exceeding the crystal's by 62. The equilibrium curve — the one the liquid follows while it can still relax — falls steadily and would reach the crystal's entropy at 152.4 kelvin. It never gets there, because the liquid falls out of equilibrium first, at a temperature that depends on how long it is given: 0.01 s/K freezes at 196.1 K with 15.61 left, 1 s/K freezes at 188.1 K with 13.03 left, 100 s/K freezes at 182.1 K with 11.03 left. Ice's residual entropy is a count and does not move; a glass's is whatever it happened to have when it stopped being able to change, and that is a property of the experiment.

The entropy that depends on how fast it was cooled

Ice's residual entropy is a count, and it comes out the same whoever measures it. A glass's does not. A glass keeps whatever entropy it happened to have when its own relaxation time crossed the experiment's, so cooling ten times more slowly leaves less behind — and extrapolating the equilibrium liquid below that point takes its entropy under the crystal's at a finite temperature, which cannot happen and does not, for a reason that is still argued about.

thermodynamics · Third law The pressure at which an oil becomes a glass. Viscosity against pressure for 4 liquids on a logarithmic axis, from Barus's rule with the pressure coefficient each one actually has. The rule is an exponential, so a gigapascal multiplies an ordinary oil's viscosity by a hundred million or more, and the curves cross the line conventionally taken to mark a glass — a million million pascal-seconds — at 1.37 GPa for a mineral oil, 0.98 GPa for a traction fluid. The vertical line is the peak pressure inside the loaded contact this figure is about, 1.32 gigapascals, computed from the Hertz solution for that geometry and load. Water is drawn for contrast: its pressure coefficient is thirty times smaller, it never approaches a glass over this range, and that is why it is useless as a lubricant in a rolling contact however clean it is. Each curve is drawn solid up to the glass line and dashed above it, because past that point the material is not a liquid and its viscosity is not what decides how it shears — the exponential continues, and the substance it was written for does not.

The oil that is a glass for a quarter of a millisecond

Every other account of viscosity here varies the temperature. Pressure does something larger and in the same direction for every liquid: viscosity rises exponentially, by a factor of ten to the eight or more at the gigapascal inside a loaded gear tooth. That is not a curiosity — it is the only reason there is a film there at all. Remove the pressure dependence from the calculation and the predicted film is five nanometres, under the roughness, and the surfaces touch.

fluids · Viscosity

Named alongside it

The objects these essays reach for when they reach for this one.

ViscosityActivation energyArrheniusContact mechanicsElasticityEntropyEquilibriumErgodicityExponentialExtrapolationFree volumeFriction

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