When fluctuating fields are confined between two surfaces, long range forces arise. A famous example is the quantum electrodynamical Casimir force that results from zero point vacuwn fluctuations confuted between two conducting metal plates'. A thermodynamic analogue is the critical Casimir force: it acts between surfaces immersed in a binary liquid mixture dose to its critical point and arises from the confiuement of con centra tion fluctuations within the thin film of fluid separating the sur faces 2 • So far, all ell:peri.mental evidence for the existence of this effect has been indirece 5 • Here we report the direct measurement of critical Casimir force between a single colloidal sphere and a flat silica surface immersed in a mixture of water and 2,6 lutidi.ne near its critical point. We use total internal reflection microscopy to detemti.ue in situ the forces between the sphere and the surface, with femtonewton resolution 6 • Depending on whether the adsorp tion preferences of the sphere and the surface for water and 2,6 lutidi.ne are identical or opposite, we measure attractive and repulsive forces, respectively, that agree quantitatively with theoretical predictions and exhibit exquisite dependence on the temperature of the system. We expect that these features of critical Casimir forces may result in novel uses of colloids as model systems.The simple act of confining a fluid can give rise to new ph en om en a not observed in the bulk. An intriguing example is the critical Casi.urir force predicted to occur in binary fluid mixtures close to their critical point; like other critical phenomena, it is characterized by universal scaling functions that depend only on the internal symmetries of the system rather than on its specific material properties' . Colloidal particles suspended in binary liquids offer a particularly interesting setting for the experintental observations of such forces. At suffi ciently small particle distances, concentration fluctuations of the solvent become confined between neighbouring colloidal surfaces and modify the pair interaction 8 • If tlte Casinlir interaction strengtlt is comparable to the thermal energy, drastic changes in the phase behaviour are expected. Reversible flocculation of silica colloids in water 2,6 lutidi.ue mixtures close to the critical point has in fact been observed 9 , and critical Casinlir forces may be invoked to explain tills phenomenon. However, flocculation was observed even far away from tlte critical point where critical fluctuations are negligible, so it cannot serve as conclusive evidence for the presence of Casi.utir forces 10 " 11 • Our experiments, ainted at directly measuring critical Casi.utir forces, use a single colloidal sphere and a planar surface immersed in a binary liquid mixture of water and 2,6 lutidine. Forces are deter mined using total internal reflection microscopy (TIRM, see Methods) 6 which allows itt situ measurements with femtonewton resolution 12 (Fig. 1). The binary liquid mixture bas a lower critical demixing point at Tc = ...
We present a versatile density functional approach (DFT) for calculating the depletion potential in general fluid mixtures. In contrast to brute force DFT, our approach requires only the equilibrium density profile of the small particles before the big (test) particle is inserted. For a big particle near a planar wall or a cylinder or another fixed big particle the relevant density profiles are functions of a single variable, which avoids the numerical complications inherent in brute force DFT. We implement our approach for additive hard-sphere mixtures, comparing our results with computer simulations for the depletion potential of a big sphere of radius R b in a sea of small spheres of radius R s near i) a planar hard wall and ii) another big sphere. In both cases our results are accurate for size ratios s = R s /R b as small as 0.1 and for packing fractions of the small spheres η s as large as 0.3; these are the most extreme situations for which reliable simulation data are currently available. Our approach satisfies several consistency requirements and the resulting depletion potentials incorporate the correct damped oscillatory decay at large separations of the big particles or of the big particle and the wall. By investigating the depletion potential for high size asymmetries we assess the regime of validity of 1 the well-known Derjaguin approximation for hard-sphere mixtures and argue that this fails, even for very small size ratios s, for all but the smallest values of η s where it reduces to the Asakura-Oosawa potential. We provide an accurate parametrization of the depletion potential in hard-sphere fluids which should be useful for effective Hamiltonian studies of phase behavior and colloid structure. Our results for the depletion potential in a binary hard-sphere mixture, with size ratio s = 0.0755 chosen to mimic a recent experiment on a colloid-colloid mixture, are compared with the experimental data. There is good overall agreement, in particular for the form of the oscillations, except at η s = 0.42, the highest value of packing fraction considered.82.70.Dd, 61.20.Gy
If a fluctuating medium is confined, the ensuing perturbation of its fluctuation spectrum generates Casimirlike effective forces acting on its confining surfaces. Near a continuous phase transition of such a medium the corresponding order parameter fluctuations occur on all length scales and therefore close to the critical point this effect acquires a universal character, i.e., to a large extent it is independent of the microscopic details of the actual system. Accordingly it can be calculated theoretically by studying suitable representative model systems. We report on the direct measurement of critical Casimir forces by total internal reflection microscopy with femtonewton resolution. The corresponding potentials are determined for individual colloidal particles floating above a substrate under the action of the critical thermal noise in the solvent medium, constituted by a binary liquid mixture of water and 2,6-lutidine near its lower consolute point. Depending on the relative adsorption preferences of the colloid and substrate surfaces with respect to the two components of the binary liquid mixture, we observe that, upon approaching the critical point of the solvent, attractive or repulsive forces emerge and supersede those prevailing away from it. Based on the knowledge of the critical Casimir forces acting in film geometries within the Ising universality class and with equal or opposing boundary conditions, we provide the corresponding theoretical predictions for the sphere-planar wall geometry of the experiment. The experimental data for the effective potential can be interpreted consistently in terms of these predictions and a remarkable quantitative agreement is observed.
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