Recently, in polymeric liquids, unexpected solid-like shear elasticity has been discovered, which gave rise to a controversial discussion about its origin (2–). The observed solid-like shear modulus depends strongly on the distance L between the plates of the rheometer according to a power law G∝L−p with a nonuniversal exponent ranging between p=2 and p=3.
Zaccone and Trachenko () 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
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 ΔG∝L−3 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 = 1V∑k1; 2) converting the k sum 1V∑k to an integral over k; and 3) representing the confinement of the sample by restricting the k integral to values |k|≥L−1.
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
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
1L∑kz for
n≠0 into a
kz integral from
kz(1)=2π/L to
kmax. This gives a
ΔG contribution proportional to
L−1 instead of
L−3.
Apart from the fact that the claimed L−3 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
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