Using time-domain thermoreflectance, we have measured the transport of thermally excited vibrational energy across planar interfaces between water and solids that have been chemically functionalized with a self-assembled monolayer (SAM). The Kapitza length--i.e., the thermal conductivity of water divided by the thermal conductance per unit area of the interface--is analogous to the "slip length" for water flowing tangentially past a solid surface. We find that the Kapitza length at hydrophobic interfaces (10-12 nm) is a factor of 2-3 larger than the Kapitza length at hydrophilic interfaces (3-6 nm). If a vapor layer is present at the hydrophobic interface, and this vapor layer has a thermal conductivity that is comparable to bulk water vapor, then our experimental results constrain the thickness of the vapor layer to be less than 0.25 nm.

Water- and alcohol-soluble AuPd nanoparticles have been investigated to determine the effect of the organic stabilizing group on the thermal conductance G of the particle/fluid interface. The thermal decays of tiopronin-stabilized 3−5-nm diameter AuPd alloy nanoparticles, thioalkylated ethylene glycol-stabilized 3−5-nm diameter AuPd nanoparticles, and cetyltrimethylammonium bromide-stabilized 22-nm diameter Au-core/AuPd-shell nanoparticles give thermal conductances G ≈ 100−300 MW m-2 K-1 for the particle/water interfaces, approximately an order of magnitude larger than the conductance of the interfaces between alkanethiol-terminated AuPd nanoparticles and toluene. The similar values of G for particles ranging in size from 3 to 24 nm with widely varying surface chemistry indicate that the thermal coupling between AuPd nanoparticles and water is strong regardless of the self-assembled stabilizing group.

We describe an optical beam deflection technique for measurements of the thermal diffusivity of fluid mixtures and suspensions of nanoparticles with a precision of better than 1%. Our approach is tested using the thermal conductivity of ethanol-water mixtures; in nearly pure ethanol, the increase in thermal conductivity with water concentration is a factor of 2 larger than predicted by effective medium theory. Solutions of C 60 -C 70 fullerenes in toluene and suspensions of alkanethiolate-protected Au nanoparticles were measured to maximum volume fractions of 0.6% and 0.35 vol %, respectively. We do not observe anomalous enhancements of the thermal conductivity that have been reported in previous studies of nanofluids; the largest increase in thermal conductivity we have observed is 1.3% ± 0.8% for 4 nm diam Au particles suspended in ethanol.

Thermal transport in aqueous suspensions of Au-core polymer-shell nanoparticles is investigated by time-resolved measurements of optical absorption. The addition of an organic cosolvent to the suspension causes the polystyrene component of the polymer shell to swell, and this change in the microstructure of the shell increases the effective thermal conductivity of the shell by a factor of approximately 2. The corresponding time scale for the cooling of the nanoparticle decreases from 200 ps to approximately 100 ps. The threshold concentration of cosolvent that creates the changes in thermal conductivity, 5 vol % tetrahydrofuran in water or 40 vol % N,N-dimethylformamide in water, is identical to the threshold concentrations for producing small shifts in the frequency of the plasmon resonance. Because the maximum fraction of solvent in the polymer shell is less than 20 vol %, the increase in the effective thermal conductivity of the shell cannot be easily explained by contributions to heat transport by the solvent or enhanced alignment of the polystyrene backbone along the radial direction.