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Do we understand the solid-like elastic properties of confined liquids?
Do we understand the solid-like elastic properties of confined liquids?

Author contributions: L.A., T.B., S.C., M.P., G.R., and W.S. performed research; and G.R. and W.S. wrote the paper.

Article Type: letter Article History
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Angelani,Bryk,Capaccioli,Paoluzzi,Ruocco,and Schirmacher: Do we understand the solid-like elastic properties of confined liquids?

Recently, in polymeric liquids, unexpected solid-like shear elasticity has been discovered, which gave rise to a controversial discussion about its origin (123). The observed solid-like shear modulus G depends strongly on the distance L between the plates of the rheometer according to a power law GLp with a nonuniversal exponent ranging between p=2 and p=3.

Zaccone and Trachenko (4) have published an article in which they claim to explain these findings by a nonaffine contribution to the liquid shear modulus. The latter is represented as

ΔGλ=L,T1Vkωp,λ2(k)ωp,λ2(k)ω2+iων, [1]
where ωp,L(k) and ωp,T(k) are the longitudinal (L) and transverse (T) phonon dispersions, and ν is a sound attenuation coefficient.

From this, the authors (4) obtain a ΔGL3 behavior by 1) observing that, for small frequencies, the ω-dependent terms are negligible, and, consequently, the nominator cancels against the denominator, from which follows that the nonaffine contribution becomes just a mode sum MS = 1Vk1; 2) converting the k sum 1Vk to an integral over k; and 3) representing the confinement of the sample by restricting the k integral to values |k|L1.

However, the authors (4) disregard the fact that the liquid is not confined inside a sphere of diameter L, but between two plates of the rheometer with gap distance L. This means that we are dealing with a slab geometry, in which the sample boundaries Lx and Ly in x and y directions are much larger than the confinement L in the z direction.

Let us assume periodic boundary conditions with respect to Lx,Ly and L. In the limit of Lx=Ly, the k sum for MS becomes

MS=1Lkzd2(ky,ky)1. [2]
The kz sum runs over discrete values labeled as kz(n)=2πn/L. One can now order the summation as n=0,±1,±2 and convert the sum 1Lkz for n0 into a kz integral from kz(1)=2π/L to kmax. This gives a ΔG contribution proportional to L1 instead of L3.

Apart from the fact that the claimed L3 prediction is at variance with the nonuniversal exponent p, we find that its derivation is in error. We feel that the origin of the observed solid-like properties of confined liquids is still elusive.

The authors declare no competing interest.

References

D. Collin, P. Martinoty, Dynamic macroscopic heterogeneities in a flexible linear polymer melt. Phys. Stat. Mech. App. 320, 235248 (2003).

H. Mendil, P. Baroni, L. Noirez, Solid-like rheological response of non-entangled polymers in the molten state. Eur. Phys. J. E 19, 7785 (2006).

D. Collin, P. Martinoty, Commentary on “Solid-like rheological response of non-entangled polymers in the molten state” by H. Mendil et al. Eur. Phys. J. E 19, 8798 (2006).

A. Zaccone, K. Trachenko, Explaining the low-frequency shear elasticity of confined liquids. Proc. Natl. Acad. Sci. U.S.A. 117, 1965319655 (2020).