Though huge thermal conductivity enhancement was observed in some magnetic fluids under an external field, the percentage of enhancement reported were largely different in similar magnetic fluids, which was quite perplexing to the scientific community. Here, we probe the role of initial cluster size and the liquid layer confinement between nanoparticles within chains that are formed under an external magnetic field, on thermal, rheological and interfacial property enhancement in model nanofluids. Three different ferrofluids containing oleic acid capped superparamagnetic magnetic nanoparticles (Fe3O4) of average crystallite sizes 9.6, 8.3 and 10.5nm (referred as S1, S2 and S3, respectively), with different polydispersity and coating thickness, synthesized by coprecipitation technique, are used in the present study. The synthesized nanoparticles were characterized by X-ray diffraction, small angle X-ray scattering (SAXS), dynamic light scattering (DLS), vibrating sample magnetometry and thermogravimetry.Thermal conductivity enhancement in samples S1 and S2 in the presence of magnetic field when the direction of field is parallel to the direction of heat flux were 127% (at 160G) and 42% (at 70G), respectively while S3 did not show significant enhancement with field. Our results suggest that in a relatively monodisperse system, nucleation occur at longer time scales and at high field strengths. On the contrary, in significantly polydisperse system, the larger particles act as nucleation centers and hence the aggregation kinetics is much faster. Under a low magnetic field strength, the particles present in S1 interact with each other and form short nanosized chains, where the growth via tip to tip aggregation is hindered by smaller particles. However in S3, larger sized particles act as nucleation centers to initiate chain formation at low field and form thick columnar structures via zippering at higher fields that lower the heat transport efficiency. Owing to the functional group, solvent molecules are trapped between the nanoparticles and the confinement of liquid molecules reduces phonon scattering at the interface. <10% enhancement in k/kf obtained when the heat flux is perpendicular to the applied field in all three systems confirms the series mode of conduction paths. For field strength of 200G, S3 showed 800% enhancement in viscosity while S1 and S2 showed negligible viscosity enhancement. S3 showed a significantly higher yield stress than S2 indicating that the field induced structures are stronger in S3.The much larger thermal conductivity enhancement in samples with very small fraction of larger clusters (with minimum polydispersity) confirm the numerical simulation results that when liquids are confined in nanochannels, long range phonons are sustained by the base fluid that enhance heat transport by lowering the Kapitza resistance. These results provide several new insights into the mechanism of heat conduction in magnetic nanofluids and ways to achieve efficient heat transfer without increasing pumping power.
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